Submitted by Pedro Barros (pedro.silvabarros@ufpe.br) on 2018-07-20T21:09:45Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Roxanny Helen de Arruda Santos.pdf: 1730292 bytes, checksum: eeccfd757b498766eb358ab80b2c14a1 (MD5) / Approved for entry into archive by Alice Araujo (alice.caraujo@ufpe.br) on 2018-07-23T17:22:28Z (GMT) No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Roxanny Helen de Arruda Santos.pdf: 1730292 bytes, checksum: eeccfd757b498766eb358ab80b2c14a1 (MD5) / Made available in DSpace on 2018-07-23T17:22:28Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Roxanny Helen de Arruda Santos.pdf: 1730292 bytes, checksum: eeccfd757b498766eb358ab80b2c14a1 (MD5) Previous issue date: 2017-03-30 / CNPQ / Os hidrocarbonetos policíclicos aromáticos (HPAs) são compostos de grande relevância ambiental, pois apresentam características mutagênicas e carcinogênicas, mesmo em concentrações muito baixas. O Estuário do Rio Goiana (PE/PB) é considerado um ambiente ainda preservado, mas está ameaçado pela ocupação urbana, agroindústria canavieira e pelas atividades de carcinicultura. O objetivo do presente trabalho foi avaliar a concentração, origem e distribuição espacial dos HPAs nas águas e sedimentos desse ambiente estuarino, associando com a hidrodinâmica local. Perfis longitudinais foram realizados na preamar e baixamar investigando a salinidade, turbidez e clorofila. Os resultados foram similares, nos dois regimes de marés. Uma zona de turbidez máxima (ZTM) foi identificada aproximadamente à 21 km da foz. As concentrações de hidrocarbonetos do petróleo dissolvidos e/ou dispersos (HPDDs) na água foram determinadas por espectrofluorescência, e variaram entre 0,20 ± 0,02 μg L⁻¹ e 0,51 ± 0,07 μg L⁻¹ equivalentes de óleo Carmópolis, e entre 0,10 ± 0,01μg L⁻¹ e 0,26 ± 0,04 μg L⁻¹ equivalentes de Criseno. As concentrações de HPDDs foram associadas ao material particulado em suspensão (MPS), resultando num acúmulo na ZTM. As concentrações de HPAs no sedimento foram determinadas através de um sistema de cromatografia gasosa acoplado a um detector de espectrometria de massas (GC/MS), e variaram entre <0,06 e 156 ng g⁻¹, classificando o Estuário do Rio Goiana como pouco contaminado. Os HPAs nos sedimentos foram correlacionados positivamente com a matéria orgânica e fração de finos e são oriundos predominantemente de fontes pirolíticas. A análise da qualidade do sedimento sugere baixa probabilidade da biota sofrer efeitos adversos. Entretanto, é necessário que seja feito um monitoramento contínuo na área, visando controlar as vias de entrada e garantindo a conservação desse sistema estuarino de grande importância econômica, ecológica e social. / Polycyclic aromatic hydrocarbons (PAHs) are compounds of great environmental relevance. They are potentially mutagenic and carcinogenic, even in very low concentration. The Goiana River Estuary (PE / PB) is still considered a well preserved environment, but may be under threaten by urban occupation, sugar cane agro industry and shrimp farming activities. The objective of the present work was to evaluate the concentration, origin and spatial distribution of HPAs in water and sediment of this estuarine environment, correlating to local hydrodynamics. Longitudinal profiles were performed during high and low tides investigating salinity, turbidity and chlorophyll. Results were similar in both tidal regimes. An estuarine turbidity maximum (ETM) was identified approximately 21 km upstream. Dissolved and/or dispersed petroleum hydrocarbons (HPDDs) in water were determined by spectrofluorescence, ranging from 0.20 ± 0.02 μg L⁻¹ to 0.51 ± 0.07 μg L⁻¹ oil Carmópolis equivalents, and between 0.10 ± 0.01μg L⁻¹ and 0.26 ± 0.04 μg L⁻¹ chrysene equivalents. HPDDs were associated with suspended particulate matter (SPM), resulting in accumulation at ETM. PAHs in the sediment were determined using a gas chromatography system coupled to a mass spectrometry (GC / MS) detector, ranging from <0.06 to 156 ng g⁻¹. This range classify the Goiana River estuary as low contaminated. PAHs in sediments were positively correlated with organic matter and fine fraction, and are predominantly derived from pyrolytic sources. Analysis of sediment quality suggests a low probability of adverse effects on biota. However, it is necessary to have continuous monitoring in the area, to control the input routes and to ensure the preservation of this estuarine system of great economic, ecological and social importance.

Submitted by Pedro Barros (pedro.silvabarros@ufpe.br) on 2018-08-08T19:43:20Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Carolina Barbosa Cabral.pdf: 930966 bytes, checksum: 096287bf2e7cc7676b00e9b36cb6b73f (MD5) / Rejected by Alice Araujo (alice.caraujo@ufpe.br), reason: on 2018-08-13T21:22:26Z (GMT) / Submitted by Pedro Barros (pedro.silvabarros@ufpe.br) on 2018-08-13T21:33:00Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Carolina Barbosa Cabral.pdf: 930966 bytes, checksum: 096287bf2e7cc7676b00e9b36cb6b73f (MD5) / Approved for entry into archive by Alice Araujo (alice.caraujo@ufpe.br) on 2018-08-17T19:18:48Z (GMT) No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Carolina Barbosa Cabral.pdf: 930966 bytes, checksum: 096287bf2e7cc7676b00e9b36cb6b73f (MD5) / Made available in DSpace on 2018-08-17T19:18:48Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Carolina Barbosa Cabral.pdf: 930966 bytes, checksum: 096287bf2e7cc7676b00e9b36cb6b73f (MD5) Previous issue date: 2017-04-24 / CNPq / Os hidrocarbonetos policíclicos aromáticos (HPAs) são compostos orgânicos prioritários em estudos ambientais devido a sua toxicidade para os sistemas biológicos. Estes são conhecidos precursores de efeitos carcinogênicos e mutagênicos para animais e humanos. O estuário do Rio Potengi/Jundiaí é o mais importante do Rio Grande do Norte e, além de sevir como berçário para diversos organismos, este abriga o Porto de Natal, terminal pesqueiro, indústrias, etc., cujas atividades podem estar ameaçando a saúde deste ecossistema. Visando investigar danos genômicos em caranguejo e associar a contaminação do sedimento por HPAs no estuário do Rio Potengi - Natal (RN), foram coletados caranguejos-uçá (Ucides cordatus) e sedimentos da sua loca em 4 diferentes estações ao longo do estuário. A contaminação dos sedimentos por HPA foi avaliada em paralelo aos efeitos genotóxicos nestes caranguejos. As concentrações de HPAs foram determinadas através do método de cromatografia gasosa acoplado a um espectrômetro de massas, e as alterações genéticas foram avaliadas pelo teste de micronúcleo (macrolesões) e ensaio cometa (microlesões). As concentrações dos HPAs totais variaram de 3,25 ng g⁻¹ a 1065 ng g⁻¹, sendo uma estação classificada como pouco contaminada, e as demais como moderadamente contaminadas. Alguns compostos apresentaram concentrações acima do nível limiar de efeito adotado pela Agência Ambiental do Canadá, sugerindo que ocasionalmente podem causar efeitos tóxicos aos organismos locais. A frequência de micronúcleos nos Caranguejos-Uçá foi significativamente maior que no controle (U. cordatus coletados na Estação Ecológica da Juréia), e correlacionaram positivamente com os HPAs, sugerindo que estes sejam potenciais agentes causadores desta genotoxicidade. Os resultados do ensaio cometa não apresentaram correlação com os HPAs e nem com a frequência de micronúcleos, sugerindo que outras variáveis ambientais e/ou compostos lançados no ambiente sejam os principais responsáveis pelas microlesões observadas. Este estudo mostra que a poluição crônica por HPAs no estuário do Rio Potengi/Jundiaí está contribuindo com danos genômicos nos U. cordatus, podendo ameaçar a conservação destes organismos, que já estão na lista de espécies sobreexplotadas ou ameçadas de sobreexplotação. A abordagem utilizada neste trabalho foi eficaz na avaliação da saúde do caranguejo-Uçá, porém estudos complementares utilizando outras classes de contaminantes e outros tipos de medidas biológicas são necessárias. / Polycyclic aromatic hydrocarbons (PAHs) are priority organic compounds in environmental studies due to their toxic potential to biological systems. They are known carcinogenic and mutagenic precursors to animals and humans. The Potengi/Jundiaí is the most important estuary in Rio Grande do Norte and, besides serving as a nursery for various organisms, it houses the Port of Natal, fishing terminals, industries, etc., that may be threatening the health of this ecosystem. This study aimed to investigate genomic damages on crabs and test the correlation with PAH contamination in sediments from Potengi estuary, in Natal (RN). Uçá-crabs (Ucides cordatus) and sediments from their burrow were collected in 4 different stations along of estuary. PAHs concentrations were determined by gas chromatograph coupled to a mass spectrometer, and the genetic alterations were evaluated by micronucleus test (macrolesions) and comet assay (microlesions). Total PAHs ranged from 3.25 ng g⁻¹ to 1065 ng g⁻¹. One station was classified as low contaminated, and the others as moderately contaminated. Some compounds showed concentrations above threshold effects level, proposed by Environment Agency of Canada, suggesting that occasionally they may cause toxic effects to local organisms. Micronuclei frequency in Uçá crabs was significantly higher than the control site (U. cordatus collected at Juréia – Itatins Ecological Station), and a positive correlation with PAHs was observed, pointing out these compounds as important stressors to the genotoxic effects observed. There was no correlation between comet assay and PAH or micronuclei frequency, indicating that some other environmental variables and/or compounds are the major responsible for the observed microlesions. This study showed that PAHs chronically introduced in the Potengi/Jundiaí estuary may threaten the conservation of U. cordatus, which is already listed as an overexploited species or under threat of overexploitation. The methodology used was efficient in the evaluation of these crabs' health, but complementary studies investigating other classes of contaminants and others biological measures are necessary.

Made available in DSpace on 2018-08-01T21:36:54Z (GMT). No. of bitstreams: 1 tese_10767_Dissertação Corrigida - Versão Final - Júlia de Almeida Leite.pdf: 16379069 bytes, checksum: f5cdfd44e4f8ccf3e78d9c10b90dc473 (MD5) Previous issue date: 2017-03-30 / A maconha é a droga ilícita mais consumida no mundo. Ela é derivada da planta Cannabis sativa L. Neste trabalho, um total de 156 amostras de maconha apreendidas no estado do Espírito Santo (ES) Brasil foram estudadas e analisadas por RMN de 1H a fim de se identificar seus principais canabinoides. Primeiramente, para se otimizar a identificação por RMN, testes de extração foram realizados com diferentes solventes e o método com a combinação metanol + maceração + clorofórmio deuterado para análises de RMN foi escolhido. Por essa técnica observou-se grande similaridade entre as amostras a partir dos espectros obtidos. Após as análises de RMN de 1H, um extrato bruto de todas as amostras foi submetido à CLAE com o objetivo de purificar esses compostos para servirem como substâncias de referência. Nove frações foram obtidas e então analisadas por RMN e CG-EM, sendo que cinco apresentaram canabinoides confirmados pela última técnica. &#916;9-THC (&#916;9-tetraidrocanabinol), &#916;9-THCA (ácido tetraidrocanabinólico), &#916;8-THC (&#916;8-tetraidrocanabinol), 11-hidroxicanabinol, CBV (canabivarina) e CBN (canabinol) foram encontrados e suas estruturas químicas confirmadas por CG-EM. O último composto foi obtido com alta pureza (&#8776;100%), podendo ser utilizado como material de referência, enquanto os outros foram obtidos como misturas menos complexas. Outros canabinoides como canabicromeno, canabiciclol e canabicumaronona foram também encontrados no extrato bruto de maconha. As 156 amostras foram também analisadas por EM e notou-se entre elas a mesma similaridade observada por RMN. A técnica quimiométrica Análise de Componentes Principais (ACP) foi aplicada aos dados obtidos por RMN e EM e o mesmo resultado foi verificado para ambas as técnicas: amostras naturalmente agrupadas indicando que as mesmas são similares. Esse fato pode sugerir a possibilidade de que toda a maconha apreendida no ES possa ser proveniente de uma mesma fonte, entrando no estado por um mesmo local e sendo então distribuída aos municípios. Para uma nova ACP aplicada aos dados de RMN, com seleção de variáveis para os espectros, foi observado um agrupamento entre as amostras ao longo dos meses, diferenciando-se em dois grupos (julho/2014 a janeiro/2015 e fevereiro/2015 a julho/2015), o que pode indicar a existência de amostras novas e antigas. Além disso, utilizando-se três frações obtidas após a purificação do extrato bruto de maconha por CLAE, para aplicação de uma ACP supervisionada, foi possível confirmar novamente o quão similares as amostras apreendias são, e também observar que o perfil químico delas apresentou uma maior similaridade com o espectro de RMN de 1H da fração isolada contendo a mistura de &#916;8-THC + &#916;9-THC + CBN.

O glifosato é o herbicida mais usado em todo o mundo. Sendo assim, é necessário que se tenham programas de monitoramento do seu uso, para garantir o bem estar da lavoura e da população. O seu metabólito principal é o ácido aminometilfosfônico (AMPA) que apesar de possuir baixa toxicidade, é mais persistente que o glifosato. O presente trabalho teve como objetivo desenvolver uma metodologia de análise para o glifosato e o AMPA por cromatografia gasosa acoplada à espectrometria de massas (CG/EM), a fim de avaliar possíveis contaminações em amostras ambientais nas imediações do Rio Monjolinho, em São Carlos. Para a faixa estudada (1,0 ug L-1 a 500 ug L-1, os limites de detecção e quantificação para o AMPA foram de 0,15 e 0,45 ug L-1 e para o glifosato, 0,67 e 2,02 ug L-1. As recuperações em água variaram entre 96,2 e 121% e para solo 70,1 a 119%. O método proposto apresentou boa linearidade, exatidão, seletividade e sensibilidade. A robustez foi avaliada de acordo com o teste de Youden. O procedimento de extração foi baseado em reações ácido-base e realizou-se etapa de clean-up para água e sedimento. Para os pontos amostrados, houve resíduo de AMPA em dois pontos (4,19 e 6,22 ug L-1). Os resultados encontrados para DBO foram altos, estando acima do limite estabelecido para um corpo d\'água Classe 3, de acordo com a CONAMA 357. Isso pode ter ocorrido devido à grande quantidade de esgoto despejado no leito do rio. Os valores de nitrogênio e fósforo também estão elevados, o que indica uma alta eutrofização do leito do rio. Vale ressaltar a necessidade de se ter uma legislação que estabeleça um limite máximo permitido para o AMPA, visto que ele é mais persistente no ambiente do que o glifosato. / The glyphosate is the most widely used herbicide worldwide. Therefore, it is necessary to have programs for monitoring their use to ensure the welfare of the farming and population. Its main metabolite is the acid aminomethylphosphonic (AMPA) that despite having low toxicity, is more persistent than glyphosate. This study aimed to develop a methodology for analyzing glyphosate and AMPA by gas chromatography coupled to mass spectrometry (GC/MS) in order to assess possible contamination of samples environment in the vicinity of Monjolinho River in São Carlos. In the range studied (1.0 ug L-1 to 500 ug L-1, limits of detection and quantification were 0.15 and 0.45 ug L-1 for AMPA and 0.67 and 2.02 ug L-1 for glyphosate. The recoveries in water varied between 96.2 and 121% and for soil from 70.1 to 119%. The proposed method showed good linearity, accuracy, selectivity and sensitivity. The robustness was evaluated according to the Youden test. The extraction procedure was based on acid-base reactions and included a clean-up step for water and sediment. For the sampling sites, it was determined residual AMPA at two points (4.19 and 6.22 ug L-1). The results for BOD were high, being above the limit set for a waterbody Class 3, according to CONAMA 357. This may be due to large amount of sewage dumped into the river bed. The values of nitrogen and phosphorus are also high, which indicates a high eutrophication of the bed river. It is worth emphasizing the need of having a legislation that establishes a maximum allowed value for AMPA, whereas it is more persistent in environment than glyphosate.

A contaminação das águas subterrâneas e recursos hídricos superficiais nas últimas décadas representam uma ameaça para a saúde pública. No Brasil, as águas subterrâneas desempenham importante papel no abastecimento público e privado, suprindo as mais variadas necessidades de água em diversas cidades e comunidades. Com a finalidade de garantir a qualidade da água consumida, o ser humano vem desenvolvendo desde a década de 70 diversas técnicas analíticas para monitorar a presença de contaminantes. No entanto, algumas dessas técnicas podem gerar resíduos piores ao meio ambiente do que as já existentes. Desta maneira a partir da década de 90, surge uma nova tendência na forma como conduzir as análises químicas, com o intuito de reduzir o impacto ambiental. No presente trabalho, foi explorada uma técnica de extração que atende tais objetivos, denominada como microextração líquido-líquido dispersivo DLLME, desenvolvida por M.Rezaee e colaboradores. Onde foram validados os hidrocarbonetos policíclicos aromáticos, atingindo limites entre 0,04 a 1,56 &mu;gL-1, também foram analisadas amostras de águas subterrâneas coletadas aleatoriamente, em 4 postos de gasolina localizados na cidade de São Paulo. / Contaminations of groundwater and surface water resources in recent decades represent a threat to public health. In Brazil, groundwater plays an important role in public and private provision, meeting the diverse needs of water in various cities and communities. In order to ensure the quality of water consumed, the human being has been developing since the 70`s analytical techniques to monitor the presence of contaminants. However, some of these techniques can generate worst waste to the environment than the existing ones. Thus from the 90\'s, a new trend in how to conduct chemical analysis, aiming to reduce the environmental impact arises. In the present study, we explored a technique for extraction that meets these goals, termed as dispersive liquid-liquid microextraction - DLLME, developed by M.Rezaee and collaborators. Where polycyclic aromatic hydrocarbons have been validated, reaching limits between 0.040 to 1.558 &mu;gL-1, also groundwater samples randomly collected from four gas stations located in the city of São Paulo analyzed.

Electrospray ionization mass spectrometry (ESI-MS) is a fast and sensitive technique that is ideal for detecting low concentration species of interest within complex mixtures. Because ESI-MS simply transfers charged species to the gas phase, only ions pre-formed in solution are visible. Accordingly, the charged tag, 3-(4-(bromomethyl)benzyl)-1-methylimidazolium hexafluorophosphate, was designed and synthesized to allow selective detection of phenols in petroleum fractions. Pressurized sample infusion (PSI) was optimized and used for time dependent analyses. PSI ESI-MS was applied to measure O-alkylation of the phenol species leading to rate information about the overall reaction along with dynamic information about reaction progress. The relative intensity of the charged tag was used to determine semi-quantitatively the presence of phenols in different petroleum fractions. Other derivatization methods in petroleomics were also explored. 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide methiodide (EDT) derivatization followed by PSI ESI-MS analysis was applied for the selective measurement and identification of naphthenic acids in petroleum fractions. The reactions of standard naphthenic acids and EDT were studied by PSI ESI-MS to assess the efficiency of EDT and the rate of reactions. The same petroleum fractions were analysed by cold Electron ionization (Cold EI) gas chromatography-mass spectrometry (GC/MS) and classical EI GC/MS. The combination spectra from the subtraction from cold EI spectra to classical EI spectra provide us a new dimension to cold EI analysis of complex matrices. Meanwhile, a Python program was written to rapidly screen cold EI GC/MS data for routine tasks, such as retention time comparison on different instrument parameters for single petroleum sample and spectrum comparison on the same retention time for different petroleum samples. / Graduate

The two additive brominated flame retardants, tetrabromoethylcyclohexane (TBECH) and hexabromocyclododecane (HBCD) are used to prevent fire to start and spread. They are simply mixed with material and are most likely to leach out in the environment, because of non-covalently binding to the material. TBECH can exist as four pairs of enantiomers, α-, β-, γ- and δ-TBECH. The technical HBCD can exist as three pairs of enantiomers, α-, β- and γ-HBCD and two meso forms δ- and ε-HBCD. None of these compounds are produced in Sweden, but they are imported to industries. TBECH has been found in Beluga blubber and can accumulate in zebrafish. HBCD has been found in water environments and can be toxic to and bioaccumulate in water-living animals. In this study, a method was developed for separation and detection of α-, β-, γ- and δ-TBECH on HRGC/HRMS. All TBECH-isomers could be separated with the developed method. How much of the TBECH isomers that were recovered after applying existing extraction and clean-up procedures, normally applied for clean-up and extraction of PCBs and PCDD/Fs, was evaluated. Low recovered amounts (6.8-35.5 %) of TBECH-isomers added in known amounts to three different whale samples indicate severe evaporation losses and possibly photolytic degradation. None of the four enantiomers were detected in the three whale samples. For HBCD analysis, both the chromatography and MS/MS parameters were optimised for δ- and ε- HBCD yielding good chromatography and sensitivity. However, due to technical difficulties during the time-period of this project, no whale samples could be analysed for HBCD on UPLC/MS/MS.

La consommation excessive d’alcool présente des risques élevés pour l’individu et pour la société ; elle est fréquemment associée à une augmentation du risque d’accidents, d’actes de violence, et peut également conduire à court et/ou à long terme à de graves maladies et à des problèmes sociaux. Dès lors, l’utilisation de marqueurs fiables permettant de détecter une consommation excessive d’alcool, ponctuelle ou chronique, s’avère nécessaire pour prévenir des conséquences néfastes de l’abus d’alcool. L’éthylglucuronide (EtG) est un marqueur d’alcoolisation utilisé en toxicologie clinique (alcoologie) et médicolégale. Par rapport aux marqueurs indirects d’alcoolisation (CDT, &#947;-GT), ce métabolite mineur de l’éthanol est très spécifique et est quantifiable dans diverses matrices biologiques. La production d’EtG est catalysée par des enzymes de la famille des UDP-glucuronosyl-transférases (UGT). Cependant, les UGT impliquées dans la glucuronoconjugaison de l'éthanol, ainsi que les sources potentielles de variabilité interindividuelle de la production d'EtG, sont encore mal connues. Nos travaux ont ainsi consisté à (1) développer et valider une méthode de dosage de l’EtG dans différentes matrices biologiques par chromatographie en phase gazeuse couplée à la spectrométrie de masse en tandem, (2) identifier les UGT humaines impliquées dans la glucuronoconjugaison de l’éthanol et étudier la contribution relative de chaque isoforme active au niveau hépatique, (3) étudier l’impact de substances fréquemment utilisées par les consommateurs d’alcool sur la production d’EtG in vitro, (4) étudier l’impact de polymorphismes génétiques fonctionnels des UGT sur la production hépatique d’EtG, et enfin (5) évaluer l’impact de la consommation de cannabis et d’autres drogues sur la production d’EtG à l’aide de prélèvements post-mortem. Ces travaux ont notamment permis de montrer que (1) l'éthanol est glucuronoconjugué principalement par le foie, puis dans une moindre mesure par les reins et par l'intestin, (2) les UGT1A9 et 2B7 sont les deux enzymes majoritairement impliquées dans la glucuronoconjugaison de l’éthanol, quel que soit l’organe considéré, (3) la morphine, la codéine, la nicotine et la cotinine n’entraînent aucune modification des taux de production d’EtG in vitro ; le lorazépam et l'oxazépam augmentent légèrement cette production (p = 0,2 et 0,065, respectivement) ; le cannabidiol inhibe la glucuronoconjugaison de l’éthanol par un mécanisme non-compétitif (CI50 = 1,17 mg/L; Ki = 3,1 mg/L), alors que le cannabinol augmente cette glucuroconjugaison de manière concentration-dépendante (p <0,05), (4) les SNP c.-900G>A affectant l’UGT2B7 et IVS1+399T>C affectant l’UGT1A9 augmentent légèrement la production d’EtG in vitro. Enfin (5) le rapport des concentrations sanguines EtG/éthanol apparaît significativement plus élevé chez des co-consommateurs de cannabis et/ou d’autres drogues que chez des consommateurs d’alcool seul. L’ensemble de ces résultats démontre l’existence de plusieurs facteurs pouvant potentiellement influencer la production d’EtG et devraient donc être pris en considération lors de l’interprétation de sa concentration in vivo. / Alcohol abuse is frequently associated with an increased risk of road accidents and violence, and can also lead to serious social and health problems. Therefore, the use of reliable markers to detect excessive punctual and/or chronic consumption of alcohol is necessary to prevent the harmful consequences of alcohol abuse. Ethylglucuronide (EtG) has been proposed as a marker of alcohol consumption in a variety of clinical and forensic contexts. Compared with the indirect markers (e.g. CDT, &#947;-GT), this minor metabolite of ethanol is very sensitive and specific, and is quantifiable in various biological matrices. It is formed by conjugation of ethanol with uridine 5’-diphosphate glucuronic acid (UDP-GA) via the action of UDP-glucuronosyltransferase (UGT) enzymes. However, the knowledge of the UGTs involved in the glucuronidation of ethanol, and the potential sources of the interindividual variability of EtG production are still not clearly established. The aims of our work were (1) to develop and validate a method for the determination of EtG in different biological matrices by gas chromatography coupled with tandem mass spectrometry, (2) to identify the human UGT isoforms involved in the glucuronidation of ethanol, and then to evaluate qualitatively and quantitatively their specific contribution in the formation of EtG, (3) to study the impact of the co-administration of drugs frequently used by ethanol consumers on the in vitro production of EtG, (4) to study the impact of functional genetic polymorphisms of two UGTs on the hepatic production of EtG, and finally (5) to study the impact of the consumption of cannabis and other drugs on the production of EtG using post-mortem samples. The main results of our study showed that (1) ethanol is primarily glucuronidated by the liver and, to a lesser extent, by kidneys, (2) UGT1A9 and 2B7 were identified as the main human UGTs involved in ethanol glucuronidation, (3) morphine, codeine, nicotine, and cotinine did not modify EtG in vitro formation rate; lorazepam and oxazepam produced a minor, but not significant, increase of EtG formation. Only cannabinol and cannabidiol significantly affected ethanol glucuronidation; cannabinol significantly increased the glucuronidation of ethanol in a concentration-dependent manner, whereas cannabidiol inhibited the glucuronoconjugaison of ethanol by a non-competitive mechanism (CI50 = 1.17 mg / L; Ki = 3.1 mg / L), (4) the SNP c.-900G>A and IVS1+399T>C affecting UGT2B7 and UGT1A9, respectively, seem to increase the in vitro production of EtG, and (5) cannabis and/or drugs consumption (mainly opioids, benzodiazepines, and paracetamol) seem to be associated with ratios of blood concentrations of EtG/ethanol significantly higher than those observed among only alcohol consumers. Taken together, these results show the existence of several factors that could potentially influence the production of EtG, and that should be taken into account when interpreting its concentration in vivo.

Soil contamination from petroleum spills is a frequent environmental problem in the world. It is obvious that petroleum exploration has contributed immensely to the economic growth of Nigeria, but over the last few decades, the Niger Delta of Nigeria has suffered grave human health risk and ecosystem degradation resulting from oil spillages, petroleum products leakages and other involuntary effluent discharges from oil exploration activities. This research seeks to develop and optimize GC-FID methods for the analysis of Petroleum hydrocarbons. Crude oil spillage contamination of soil from the Niger Delta was investigated 3 months after a crude oil-pipeline spillage. 47 Soil samples (300-500g) were collected at several points in the South-South Niger Delta. Control samples were taken from four unaffected sites within the vicinity of spillage with similar soil characteristics. Samples were collected at depths of 0-15 cm, 15-30 cm and 30-60 cm. The soil samples were prepared for analysis using solvent extraction methods, passed through column of sodium sulphate and Florisil® to aid in column performance, remove moisture and gross impurities. Samples were analysed using gas chromatography with a flame ionisation detector. Penetration and migration of C10-C26 and C26-C34 hydrocarbons through the soil layers were assessed by cluster analysis to determine the spatial distribution, penetration and chemical similarity of these compounds over the contaminated area. This information is a useful guide for bioremediation purpose. It was found that total petroleum hydrocarbon concentrations varied from 9-289 mgkg-1 topsoil, 8-318 mgkg-1 subsoil and 7-163 mgkg-1 at the greatest depth measured.The results show elevated levels of total hydrocarbon contents when compared with the reference sites. Drastic steps should be taken to carefully monitor and remediate the environment. Bioremediation with plants and micro-organisms is endorsed.

Gunshot residue (GSR) is the term used to describe the particles originating from different parts of the firearm and ammunition during the discharge. A fast and practical field tool to detect the presence of GSR can assist law enforcement in the accurate identification of subjects. A novel field sampling device is presented for the first time for the fast detection and quantitation of volatile organic compounds (VOCs). The capillary microextraction of volatiles (CMV) is a headspace sampling technique that provides fast results (< 2 min. sampling time) and is reported as a versatile and high-efficiency sampling tool. The CMV device can be coupled to a Gas Chromatography-Mass Spectrometry (GC-MS) instrument by installation of a thermal separation probe in the injection port of the GC. An analytical method using the CMV device was developed for the detection of 17 compounds commonly found in polluted environments. The acceptability of the CMV as a field sampling method for the detection of VOCs is demonstrated by following the criteria established by the Environmental Protection Agency (EPA) compendium method TO-17. The CMV device was used, for the first time, for the detection of VOCs on swabs from the hands of shooters, and non-shooters and spent cartridges from different types of ammunition (i.e., pistol, rifle, and shotgun). The proposed method consists in the headspace extraction of VOCs in smokeless powders present in the propellant of ammunition. The sensitivity of this method was demonstrated with method detection limits (MDLs) 4-26 ng for diphenylamine (DPA), nitroglycerine (NG), 2,4-dinitrotoluene (2,4-DNT), and ethyl centralite (EC). In addition, a fast method was developed for the detection of the inorganic components (i.e., Ba, Pb, and Sb) characteristic of GSR presence by Laser Induced Breakdown Spectroscopy (LIBS). Advantages of LIBS include fast analysis (~ 12 seconds per sample) and good sensitivity, with expected MDLs in the range of 0.1-20 ng for target elements. Statistical analysis of the results using both techniques was performed to determine any correlation between the variables analyzed. This work demonstrates that the information collected from the analysis of organic components has the potential to improve the detection of GSR.