O estudo objetivou desenvolver e validar um método para identificar e quantificar poluentes orgânicos persistentes, conhecidos como POPs, em solo de regiões industriais dos municípios de Caieiras e Franco da Rocha SP, via cromatografia a gás acoplada a Espectrometria de Massas (GC-MS) e Detector por Captura de Elétrons (ECD). Em observância ao Tratado de Estocolmo, patrocinado pela Organização das Nações Unidas ONU, que prevê o banimento de pelo menos doze dos POPs, e no qual o Brasil é um dos 113 países signatários, o trabalho visou colaborar positivamente com essa questão ambiental tão importante. Estes compostos são tóxicos e altamente estáveis no ambiente e em organismos vivos, dentre os quais, são abordados nesse trabalho o clordano cis/trans (C10H6Cl8), o heptacloro (C10H5Cl7), o heptacloro epóxido cis/trans (C10H5Cl7) e os isômeros α-, β-, γ- e δ-BHC (C6Cl6). Para garantir a confiabilidade das análises realizadas, foram realizados ensaios de Validação da metodologia, com base nas diretrizes do INMETRO. A técnica de extração utilizada foi o QuEChERS, obtendo resultados de recuperação na faixa de 70 a 120% para a maioria dos compostos estudados, considerados aceitáveis para matrizes complexas. Os limites de detecção e quantificação do método compreenderam a faixa de 0,0002 e 0,01 μg.g1, respectivamente. As amostras analisadas apresentaram contaminação pelos compostos hexaclorobenzeno α-, β-, γ- e δ-, muitas das quais estão acima dos limites máximos permissíveis, de acordo com as legislações nacionais e internacionais vigentes. / The study aimed to develop and validate a method to identify and quantify persistent organic pollutants, known as POPs in soil of industrial regions Caieiras and Franco da Rocha municipalities in São Paulo, via gas chromatography coupled with Mass Spectrometry (GC-MS) and Electron Capture Detector (ECD). In compliance with the Treaty of Stockholm, sponsored by the United Nations - UN, which provides for a ban of at least twelve POPs, in which Brazil is one of the 113 signatory countries, the work aims to contribute positively to the environmental issue as important . These compounds are highly toxic and stable in the environment and living organisms, among which are address in this work chlordane cis / trans (C10H6Cl8), heptachlor (C10H5Cl7), heptachlor epoxide the cis / trans (C10H5Cl7) and the isomers α-, β-, γ- and δ-BHC (C6Cl6). To ensure reliability of the analysis carried out, tests were carried out validation method, based on the guidelines of INMETRO. The extraction technique was used QuEChERS, achieving recovery in the range 70 to 120% for the most of compounds, acceptable for complex matrices. The limits of detection and quantification of the method comprises the range of 0.0002 and 0.01 μg.g-1, respectively. The samples analyzed were contaminated by compounds hexachlorobenzene α-, β-, γ- and δ-, many of which are above the maximum allowable in accordance with national legislation and international law.

O presente trabalho teve como objetivo determinar, por meio da Cromatografia Gasosa acoplada à Espectrometria de Massas (CG-MS), produtos oriundos da degradação do digluconato de clorexidina (CHX) 2 % em gel. Foram selecionados três géis: comercial Gel_Chlorhexidina® (Maquira), CHX gel UNIARARAS (Manipulado pela Farmácia Ensino Uniararas) e gel CHX 2 % preparado a partir de uma uma solução comercial de CHX 20 % Sigma® no laboratório. Para que fosse possível comparar os resultados, foi preparada uma solução de CHX 2 % partindo da mesma solução comercial de CHX Sigma®. Para a avaliação dos produtos de degradação da CHX 2 %, os géis e a solução foram pesados (1 g / gel 1 mL /solução) e acondicionados em tubos plásticos (Eppendorf®). Os tubos foram subdivididos em quatro diferentes situações de armazenamento (sobre a bancada de trabalho com e sem a presença de luz, em forno de Pasteur a 36,5 °C sem luz e em geladeira a 8 °C sem luz) e quatro diferentes períodos de análise (inicial, após 1 mês, 3 meses e 6 meses de armazenamento) resultando em 52 análises cromatográficas. Após o período determinado, as amostras foram extraídas, filtradas e analisadas por meio de CG-MS. Os resultados mostraram, na análise inicial, que todos os géis e a solução já continham produtos de degradação da CHX (espécies de oxigênios reativos - ROS). Um dos ROS era a pCA. Além da pCA, outros ROS foram observados, oCA e/ou mCA (isômeros da pCA) e os organoclorados orto-isocianato clorofenil e 2-amino-5-clorobenzonitrila. A porcentagem de pCA calculada nas amostras dos géis não foi gradual nem uniforme, levantando a hipótese de falta de homogeneidade da CHX na formulação do gel. A não homogeneidade foi comprovada através de análise em espectrofotometria UV/Vis. Uma sugestão de manipulação dos géis de CHX foi então sugerida e a homogeneidade da CHX nos géis manipulados desta maneira foi comprovada através de análise em espectrofotometria UV/Vis. Concluiu-se que os géis e a solução de CHX a 2 % analisados neste trabalho, apresentaram produtos oriundos da degradação da CHX em todas as situações de armazenamento e tempo de análises propostas, essa degradação é um problema intrínseco da CHX. Os produtos formados a partir da oxidação da CHX são tóxicos e possuem características genotóxicas, podendo trazer riscos ao seres humanos com danos celulares e no DNA. Mais estudos são necessários para verificar o potencial carcinogênico da CHX, de seus produtos de degradação e se o uso de produtos contendo CHX é seguro em seres humanos. / The aim of this study was to determine, by means of gas chromatography coupled to mass spectrometry (GC-MS), products originated from the degradation of 2 % chlorhexidine digluconate (CHX) gel. Three gels were selected: commercial Gel_Chlorhexidina® (Maquira), 2 % CHX gel UNIARARAS (handled at the Pharmacy Education UNIARARAS) and 2% CHX gel prepared in laboratory from a commercial 20% CHX solution (Sigma®). For comparison of the results, a 2% CHX solution was also prepared from the same commercial 20 % CHX solution (Sigma®). For assessment of the products of 2 % CHX degradation, the gels and the solution were weighed (1 g / gel - 1 mL / solution) and placed in plastic tubes (Eppendorf®). The tubes were divided into four different storage conditions (on the workbench with and without the presence of light, Pasteur oven at 36.5 °C without light and in a refrigerator at 8 °C without light) and four different evaluation periods (initial and after 1 month, 3 months and 6 months of storage), resulting in 52 chromatographic analyses. After the specified evaluation periods, the samples were extracted, filtered and analyzed by GC-MS. The results showed that, in the initial analysis, all gels and the solution already contained CHX degradation products (reactive oxygen species - ROS). One of the ROS was para-chloroaniline (pCA). In addition to pCA, other ROS were observed, oCA and/or mCA (pCA isomers) as well as the organochlorines ortho-chlorophenyl isocyanate and 2-amino-5-chloro-benzonitrile. The percentage of pCA calculated in the CHX gel samples was neither gradual nor uniform, raising the possibility of lack of homogeneity in gel formulation. The lack of homogeneity was confirmed by UV/Vis spectrophotometry. Changes in the preparation of the CHX gels were suggested, and the homogeneity of the CHX gels prepared following the suggestions was confirmed by UV/Vis spectrophotometry. It was concluded that the 2% CHX gels and solution evaluated in this study presented products from CHX degradation in all storage conditions and evaluation periods, and this degradation is an intrinsic problem of CHX. The products formed from the oxidation of CHX are toxic and have genotoxic characteristics, and may pose risks for humans such as damage to cells and DNA. Further studies are required to determine the carcinogenic potential of CHX and its degradation products and whether the use of products containing CHX in humans is safe.

A presença de nove ésteres (acetato de etila, butanoato de etila, hexanoato de etila, lactato de etila, octanoato de etila, nonanoato de etila, decanoato de etila, octanoato de isoamila e dodecanoato de etila) foi investigada por cromatografia gasosa hifenada à espectrometria de massas via injeção direta de amostras (ID-CG-EM). Cento e trinta e seis amostras de aguardente de cana foram coletadas durante sua destilação em diferentes produtores em diferentes cidades localizadas no interior do estado de São Paulo. Também foram analisadas 21 amostras de cachaça comercial, 10 amostras de rum e 10 amostras de uísque importados e obtidos em lojas \"duty free shop\". A metodologia analítica desenvolvida para análise de ésteres demonstrou-se apropriada para a determinação destes compostos em bebidas destiladas, sendo simples (injeção direta), seletiva e relativamente rápida. Apresentou baixos limites de detecção e quantificação e boa repetibilidade. O acetato de etila é o principal éster presente nas bebidas destiladas seguido pelo lactato de etila. Em todas as amostras de bebidas destiladas analisadas neste trabalho foi detectada a presença do éster lactato etila. A presença deste éster está relacionada com a contaminação do mosto por bactérias (Lactobacillus spp) responsáveis pela fermentação láctica. A concentração de lactato de etila nas amostras de cachaça e rum é muito superior à encontrada nas amostras de uísque. A análise multivariada dos resultados analíticos aplicada ao banco de dados dos ésteres juntamente com as concentrações de carbamato de etila e benzaldeído levaram à formação de dois grupos bem distintos: amostras destiladas em alambiques de cobre e amostras destiladas em colunas de aço inox. Os modelos estatísticos gerados pelas análises exploratórias de PCA, PLS e LDA utilizando o carbamato de etila, benzaldeído, decanoato de etila e o dodecanoato de etila como discriminantes revelaram ser possíveis a diferenciação entre estes dois grupos de destilados com uma porcentagem de acerto de 81% para PCA, 78,4 % para a PLS e 97,6% para LDA. Os métodos cromatográficos sugeridos pelo Ministério da Agricultura, Pecuária e Abastecimento (MAPA) para a determinação de ésteres não englobam o monitoramento do lactato de etila, subestimando o resultado final. / The presence of nine esters (ethyl acetate, ethyl butanoate, ethyl hexanoate, ethyl lactate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, isoamyl octanoate, and ethyl dodecanoate) was investigated by gas chromatography hyphenated to a mass spectrometry through sample direct inject (DI-GC-MS). One hundred and thirty six sugar cane spirits collected immediately after its distillation from different producers and different cities located in the countryside of São Paulo state. Also, it was analyzed 21 commercial samples of cachaça, 10 samples of rum and 10 samples of whiskey imported and purchased from the duty free shop. The analytical method applied to esters analysis was appropriated for the determination of these compounds in distilled spirits, since it is simple (direct inject), selective and reasonably fast. It presented low detection and quantification limits and good reproducibility. Ethyl acetate is the main ester present in the distilled spirits followed by ethyl lactate. Ethyl lactate was detected in all the distilled beverage samples analyzed herein. The occurrence of this ester is related to bacterial contamination of must (Lactobacillus spp) responsible for the lactic fermentation. The ethyl lactate content in cachaça and rum samples are superior that presented by whiskey samples. The multivariate analysis of the analytical results applied to the esters data set jointly with the content of ethyl carbamate and benzaldehyde lead to the clustering of two quite distinct groups: sugar cane spirits distilled in copper alembic and sugar cane spirits distilled in stainless steel column. The resulting statistical model generated by PCA, PLS and LDA exploratory analysis employing ethyl carbamate, benzaldehyde, ethyl decanoate, and ethyl dodecanoate as discriminators was able to distinguish between these two groups with a accuracy of 81 % for PCA, 78,4 % for PLS and 97,6 % for LDA. The chromatographic method recommended by the Ministério da Agricultura, Pecuária e Abastecimento (MAPA) for the esters determination does not include the monitoring of ethyl lactate leading to a underestimating of the final result.

A adição de diferentes substâncias (adulterantes e diluentes) no crack (freebase) é um fenômeno bem conhecido no mercado ilícito. Os adulterantes podem interagir com a cocaína e determinar novas e desconhecidas síndromes tóxicas influindo no estado clínico das intoxicações, especialmente em casos em que houve modificação das vias de administração. No Brasil a análise de adulterantes, contaminantes e/ou diluentes adicionados ao crack não constitui rotina nos laboratórios oficiais. Nesse contexto, o presente trabalho pretendeu a caracterização de um grupo de amostras de crack que fornecerá informações na investigação sobre o narcotráfico, no estudo da morbi-letalidade, bem como na toxicovigilância. O método utilizado neste trabalho foi realizado com a técnica de cromatografia gasosa acoplada a detector em ionização de chamas CG-DIC. Os resultados obtidos nas análises de amostras provenientes de apreensões realizadas na região metropolitana de São Paulo num período de 20 meses, no período de março de 2008 a novembro de 2009, mostraram que 9,16% das amostras continham lidocaína, benzocaína e cafeína como adulterantes e 14,57% continham outros adulterantes totalizando 23,73%. O percentual em teor médio de cocaína presentes nas amostras de crack foi de 71,3%. Adicionalmente foram avaliadas as propriedades organolépticas. O resultado das análises das amostras estudadas mostrou maior teor de cocaína em relação à cocaína comercializada na forma de sal (cloridrato ou sulfato) comercializado como \"droga de rua\" no Estado de São Paulo. Ainda, os interferentes e adulterantes encontrados nas amostras estudadas permitem a inferência do importante problema de saúde pública advindos do uso dessa droga. / The addition of different substances (contaminants and fillers) in the crack (freebase) is a well known phenomenon in the illicit market. The contaminants can interact with cocaine and identify new and unknown toxic syndromes influencing the clinical state of intoxication, especially in cases where there was a modification of the routes. In Brazil, the analysis of adulterants, contaminants and / or extenders added to the crack is not routine in official laboratories. In this context, this work aims to characterize a sample group of crack that provides information on an investigation into drug trafficking in the study of morbidity and mortality, as well as toxicological. The method used in this study utilized the technique of gas chromatography coupled with flame ionization detector GC-FID. The analysis results of samples from seizures made in the metropolitan region of Sao Paulo in a period of 20 months, from March 2008 to November 2009 showed that 9.16% of the samples contained lidocaine, benzocaine, and caffeine as adulterants and 14.57% contained other adulterants totaling 23.73%. The average content in percentage of cocaine present in the samples of crack was 71.3%. Additionally, we evaluated the organoleptic properties of the row samples. The results of analysis of the samples tested showed higher levels of cocaine in the cocaine sold in the form of salt (hydrochloride or sulfate) marketed as \"street drug\" in the State of São Paulo. Still, the interferences and adulterants found in the samples studied allow the inference of important public health problem arising from the use of this drug.

Os éteres difenílicos polibromados (PBDEs) são compostos amplamente utilizados como retardantes de chamas que foram introduzidos por volta da década de 1970, em uma gama de produtos industrializados, especialmente em aparelhos eletrônicos. No entanto, em contrapartida ao seu papel benéfico como dispositivo de segurança, esses compostos apresentam uma estrutura química que proporciona ao homem preocupantes efeitos tóxicos que, de acordo com vários estudos, são responsáveis por desencadearem problemas neurotóxicos e hormonais, assim como influenciarem no desenvolvimento de algumas doenças. Além disso, suas características físico-químicas permitem que eles sejam bioacumulados e persistentes no meio ambiente. Diante desses fatores, tornam-se importantes estudos que melhor caracterizem o mecanismo de ação desses compostos e, portanto, a proposta do projeto foi analisar os efeitos do congênere 2, 2\' ,3, 3\' ,4, 4\' ,5, 5\' ,6, 6\' decabromodifenil éter (BDE-209) em células de hepatocarcinoma humano do tipo HepG2, aplicando como método de análise os ensaios de citotoxicidade durante indução autofágica. Os resultados obtidos mostraram que o BDE-209, como observados em outros estudos do nosso laboratório, não apresentou toxicidade acentuada em comparação aos outros congêneres, pois mostrou resultados significativos apenas nas maiores concentrações. A indução autofágica, por sua vez, não proporcionou efeitos protetivos contra a citotoxicidade do BDE, pelo contrário, ela foi capaz de perturbar ainda mais a homeostasia celular e de causar necrose na presença de 25 µmol.L-1 do congênere. Suplementariamente, foram coletadas amostras de sedimentos provenientes de uma lagoa pertencente à área de recarga do aquífero Guaraní no município de Ribeirão Preto para a quantificação de PBDEs com o objetivo de determinar o nível de contaminação desse ambiente. Estas amostras foram analisadas por cromatografia gasosa com detector por captura de elétrons (CG-ECD), após um processo de extração, clean up e pré-concentração. Os resultados obtidos mostraram a presença de seis BDEs com somatórias de suas concentrações nos valores de 4,03 ng.g-1 e 5,38 ng.g-1 em duas amostras coletas, tendo como congênere em destaque o 2, 2\', 4, 4\' tetrabromodifenil éter (BDE-47). / The polybrominated diphenyl ethers (PBDEs) are compounds widely used as flame retardants, introduced around 1970, in a diversity of industrial products especially electronics. However, in contrast to its beneficial role as a safety device, these compounds have a chemical structure, which provides to humans worrisome toxic effects, because according to several studies, they are responsible for triggering neurotoxic and hormonal problems, as well as influence in the development of some diseases. Moreover, its chemical composition allows them to be bioaccumulated, which gives potential effects, since they are persistent in the environment. Given these factors, studies that can better describe these compounds action mechanism are important. Therefore, the proposal of this project was to analyze the effect of 2, 2\' ,3, 3\' ,4, 4\' ,5, 5\' ,6, 6\'-decabromodiphenyl ether (BDE-209) using as model the human hepatocellular carcinoma cells, HepG2, applying cytotoxicity assays during autophagic induction. The results showed that BDE-209, as observed in other studies of our group, induced no severe toxicity like other congeners as it showed significant results only in higher concentrations. The autophagic induction had no protective effects against the BDEs cytotoxicity, on the contrary, it was able to affect cells homeostasis and cause necrosis in the presence of 25 mol.L-1 of the congener. Additionally, sediment samples were collected from a recharge point of Guaraní aquifer in Ribeirão Preto for quantification of these compounds to determine the level of contamination in this environment. These samples were analyzed by gas chromatography with electron capture detector (CG-ECD) after a process of extraction, clean up and preconcentration. The results showed the presence of six BDEs with total concentration of 4.03 ng.g-1 and 5.38 ng.g-1 in two samples collected, which the main congener was 2, 2\', 4, 4\' tetrabromodiphenyl ether (BDE-47).

In this research project, real natural strawberries bought from different local sources were profiled by gas chromatography-mass spectroscopy (GCMS). These profiles were then used as a reference to compare GCMS profiles of commercial artificial strawberry flavor products such as strawberry flavored Cool Splashers™, Gatorade®, and Aquacal® flavored water. The chromatograms obtained were patterned using simple visual observations, scatter plot designs, Mann-Whitney U Test, and correlation coefficients. The artificially flavored commercial products tend to have simpler chromatograms. The Burger King® milkshake, Gatorade®, and Hi-C® are the most similar to that of the natural strawberry flavor. Their correlation coefficients are 0.972, 0.870, and 0.984 respectively. The Mann-Whitney U Test results also support the conclusions from correlation coefficients. However, the natural products tend to have more constituents including the main flavoring compounds. Thus fresh produce have better flavor and are more nutritious for a good reason.

In plants, change in lipid composition is a common response to various abiotic stresses. Lipid constituents of bryophytes are of particular interest as they differ from that of flowering plants. Unlike higher plants, mosses have high content of very long-chain polyunsaturated fatty acids. Such lipids are considered to be important for survival of nonvascular plants. Here, using abscisic acid (ABA )-induced changes in lipid composition in Physcomitrella patens as an example, a protocol for total lipid extraction and quantification by gas chromatography (GC) coupled with flame ionization detector (FID) is described.

Early research into the stable hydrogen isotopic compositions (δD) of petroleum involved bulk deuterium/hydrogen (D/H) measurements which, while providing some useful information, had to contend with the analysis of complex mixtures of hydrocarbons, and alteration resulting from the rapid exchange of nitrogen-, oxygen- and sulphur-bound hydrogen. The use of gas chromatography-isotope ratio mass spectrometry (GC-irMS) overcomes these problems by allowing the analysis of individual compounds containing only the most isotopically conservative aliphatic carbon-bound (C-bound) hydrogen. This project investigates the geochemical utility and reliability of compound-specific δD values, with the aim to better understand and exploit this analytical capability. To demonstrate the source diagnostic potential of compound-specific δD values, normal and branched alkanes extracted from series of immature bog-head coals (torbanites) were analysed. The torbanites contain immature organic matter predominantly from a single, freshwater algal source, i.e. Botryococcus braunii (B. braunii). The δD values of n-alkanes reflect the climate regime at the time of deposition of the torbanites, and vary mainly in response to the δD values of the source meteoric waters in their depositional environments. n-Alkanes from torbanites deposited at high latitude in a glacial climate are depleted in D by up to 70% relative to those from a torbanite deposited at low latitude under a tropical climate regime. Torbanites deposited in a mid-latitude region under cool-temperate conditions contain n-alkanes with δD values falling in between those of n-alkanes from tropical and glacial torbanites. / The δD values of the n-alkanes also reflect their multiple source inputs. For example, a saw-toothed profile of n-alkane δD values in Australian torbanites is attributed to a dual-source system: a predominant B. braunii input, with a minor terrestrial plant input to odd-carbon-numbered n-alkanes in the range n-C20 [subscript] to n-C29 [subscript]. The δD values of n-alkanes and isoprenoids (pristane and phytane) differ significantly in two Permian torbanites from Australia, thought to be reflective of the offset between the δD values of their precursors in extant organisms. The torbanite data indicate that a biological δD signal has been preserved for at least 260–280 million years, extending the utility of δD values for palaeoclimate studies. To elucidate the effect of sedimentary processes on the δD values of petroleum hydrocarbons, three sedimentary sequences have been studied. These comprise one from the Perth Basin (Western Australia) and two from the Vulcan Sub-basin (northern Australia) covering a wide range of maturities, i.e. 0.53–1.6% vitrinite reflectance (Ro). The δD values of n-alkanes extracted from immature-early mature sediments (marine shales/siltstones and mudstones) are consistent with that expected of marine-derived n-alkyl lipids. The hydrocarbons become enriched in D with increasing maturity. The large (ca. 115%) biologically-derived offset between the δD values of n-alkanes and acyclic isoprenoids from immature sediments gradually decreases with increasing maturity, as the isoprenoids become enriched in D more rapidly than the n-alkanes. The D-enrichment in isoprenoids correlates strongly with Ro and traditional molecular maturity parameters. / This suggests that H/D exchange during maturation occurs via a mechanism involving carbocation-like intermediates, which proceeds more rapidly with compounds containing tertiary carbon centres. Significant epimerisation of pristane and phytane coincides with their D-enrichment, suggesting that hydrogen exchange occurs at their tertiary carbons. A mechanism is proposed which can account for both H/D exchange and the epimerisation of pristane and phytane in the sedimentary environment. Pristane and phytane extracted from a post-mature sediment from the Paqualin-1 sequence are significantly enriched in D (ca. 40%) relative to the n-alkanes, indicating that D-enrichment persists at very high maturity, and is more pronounced for the regular isoprenoids than the n-alkanes. This supports the notion that H/D exchange causes the observed shift in δD values, rather than free-radical hydrogen transfer. The differences between the δD values of pristane and phytane show opposite trends in the Perth Basin and Vulcan Sub-basin sediments. In the Perth Basin, phytane is enriched in D relative to pristane, likely due to a dominant algal source. In the Vulcan Sub-basin, pristane is enriched in D relative to phytane, and thus is attributed to a lower relative input of algal organic matter. The variance of the δD values of pristane and phytane is generally consistent throughout the maturity range and provides evidence that pristane and phytane exchange hydrogen at similar rates. δD analysis of crude oils and condensates reservoired in the Perth Basin and Vulcan Sub-basin has been carried out to evaluate potential applications in oil-source correlation. / The n-alkanes from crude oils and condensates are often more enriched in D than n-alkanes extracted from their supposed source rocks, and the oils also show relatively small differences between the δD values of n-alkanes and isoprenoids. These results suggest significant H/D exchange has occurred, implying that the liquids were generated from mature source rocks. A Perth Basin crude oil (Gage Roads-1) thought to be derived from a lacustrine/terrestrial source contains hydrocarbons that are significantly depleted in D relative to Perth Basin oils derived from a marine source, attributed to variability in the isotopic composition of marine and terrestrial source waters. δD values of n-alkanes from Vulcan Sub-basin crude oils and condensates are largely consistent with their prior classification into two groups: Group A, having a marine source affinity; and Group B, having a terrigenous source affinity. Some oils and condensates are suggested to be mixtures of Group A and Group B hydrocarbons, or Group A hydrocarbons and other as yet unknown sources. An exception is a former Group A oil (Tenacious-1) containing n-alkanes that are enriched in D relative to those from other Group A oils and condensates, attributed to mixing with another source of more mature hydrocarbons. The n-alkane δD profile appears to be indicative of source and sedimentary processes. One Perth Basin crude oil (Dongara-14) contains lower-molecular-weight n-alkanes that are depleted in D relative to higher-molecular-weight n-alkanes, attributed to a mixed marine/terrestrial source. / Group A crude oils and condensates from the Vulcan Sub-basin display a ‘bowl-shaped’ profile of n-alkane δD values. An upward inflection in the n-alkane δD profile from n-C11 [subscript] to n-C15 [subscript] is suggested to represent the addition of D-enriched lower-molecular-weight n-alkanes from a more mature wet gas/condensate to an initial charge of lower maturity oil. Ultimately, this project has demonstrated that the δD values of individual petroleum hydrocarbons can be used to elucidate the nature of source organic matter and depositional environments. The preservation potential of lipid δD values is greater than previously thought, although it is clear that H/D exchange accompanying maturation can have a significant effect on the δD values of certain hydrocarbons. Thus, great care must be taken when interpreting δD values of individual hydrocarbons, particularly those derived from sediments of high thermal maturity.

An analytical method was developed for the determination of the â-agonists clenbuterol, cimaterol and salbutamol in bovine retina. The method involved extraction into a pH 8.5 tris-HCl buffer, followed by protease enzyme digestion and immunoaffinity column cleanup before analysis by liquid chromatography with tandem mass spectrometry detection LC/MS/MS. The LOD for clenbuterol, salbutamol and cimaterol were 0.64, 1.20 and 1.92 ng/g respectively. The identities of the analytes were able to be confirmed to an acceptable standard. An analytical method was also developed for the analysis of the â-agonists clenbuterol, salbutamol, cimaterol, ractopamine, and mabuterol in bovine urine and emu muscle. The urine and muscle samples were digested with â-glcuronidase enzyme and cleaned up using a Bond Elute Certify SPE. The extracts were analysed by LC/MS/MS. Deuterated internal standards were used for quantitation. The LOD for urine [less than] 1ng g and for emu muscle it was [less than] 0.3 ng/g. The last part of the work describes the simultaneous gas chromatography-mass spectrometric analysis of diethylstilbestrol DES, hexestrol HEX, dienestrol DIEN, zeranol ZER, taleranol TAL and zeralenone ZON in fresh full cream and fresh skim milk. The analytes were analysed as their trimethyl silane (TMS) derivatives. A three phase solvent system was used for extraction and the extract was cleaned up using a combination of the anion exchange and hydrophobic properties of an anion exchange SPE. The detection limits for DES, DIEN, HEX, ZER, TAL and ZON were 9.6, 9.6, 16.8 , 7.2 , 13.5 and 34.8 ng/L respectively. / Doctor of Philosophy(PhD)

Hops (Humulus lupulus L.) are an indispensable component of beer, with the essential oil responsible for imparting distinctive odour and aroma characteristics to beer. However, not all character-impact odorants in hop essential oil have been identified and hop aroma in beer is still not completely understood. The composition of hop essential oil is very complex with 485 compounds currently identified in the literature, and recent research suggests that up to 1000 compounds may actually be present. Only a certain number will be present at concentrations above threshold and make a direct contribution to the odour of the oil. In addition, many important odorants are only present at trace concentrations. Gas chromatography-olfactometry (GC-O) using human assessors is the best way to locate potent odorants and facilitate their identification. A novel methodology was developed to identify the character-impact odorants in hop essential oil samples using hyphenated techniques in gas chromatography. GC-O was used to locate odour active compounds and determine relative importance using CharmAnalysis[TM] according to the odour potency principle. Due to the chemical complexity of the samples, considerable co-elution of peaks occurs during single column gas chromatography (1DGC), making the detection and identification of character-impact odorants challenging. Therefore, comprehensive two-dimensional gas chromatography (GCxGC) combined with time-of-flight mass spectrometry (TOFMS) was used to resolve and identify compounds eluting in the odour active regions. The methodology was developed in a case study on coriander (Coriandrum sativum) and wild coriander (Eryngium foetidum) leaf essential oils. During GC-O analysis of these samples it was recognised that odour active regions frequently coincide with several co-eluting compounds. To address this, a heart-cut multidimensional gas chromatography-olfactometry (MDGC-O) instrument was developed to resolve these 'co-eluting odour clusters' and determine the compound(s) responsible for the odour perception. The 'spicy' character of hops is considered to be a desirable attribute in beer associated with 'noble hop aroma'. However, the compounds responsible have yet to be adequately elucidated. This character was investigated using a commercial 'Spicy' fraction of hop essential oil, selectively enriched for monoterpene and sesquiterpene alcohols. The odour active compounds in (i) the spicy fractions and (ii) the whole essential oils of four different hop varieties were compared using the presented methodology. A compound with an intense 'woody, cedarwood' odour was determined to be a potent, character-impact odorant in all samples. This odour coincided with a complex region of the chromatogram where up to thirteen compounds were co-eluting. The peak responsible for this odour was determined by (i) correlation of peak areas with odour potency (Charm) values and (ii) MDGC-O. The compound was tentatively identified by GCxGC-TOFMS as 14-hydroxy-β-caryophyllene, which has not previously been reported as an odorant in hop essential oil. It was concluded that this compound and other 'woody, cedarwood' odorants contributed to the 'spicy' character of the investigated hop samples. Compounds previously associated with noble hop aroma, notably caryophyllene oxide, humulene epoxides I and II, and humulenol II, did not contribute to the odour character of the hop samples. Other potent odorants that were identified in the whole essential oil and spicy fractions of hops were: geraniol, linalool, β-ionone, eugenol, isovaleric acid, and β-damascenone. While myrcene was a moderately potent odorant in the whole hop essential oil samples, the abundant sesquiterpene hydrocarbons α-humulene, β-caryophyllene and β-farnesene did not significantly contribute to the odour character.