An Ultraviolet to Visible (UV-Vis) spectroscopic analysis based on fuzzy logic approach has been developed for furan content measurement in transformer oil. Following the successful identification and quantification of furan derivatives in transformer oil by ASTM D5837 standard, the new approach is able to approximate the furan content more conveniently and economically. As furan concentration level would determine the absorption intensity in UV-Vis spectral range, the fuzzy logic software model developed would exploit this characteristic to aggregate the furans content level in transformer oil. The UV-Vis spectral response at other ambient temperature is also studied. The proposed technique provides a convenient alternative to conventional method of furan measurement by High Performance Liquid Chromatography (HPLC) or Gas Chromatography Mass Spectrometry (GC/MS) in ASTM D5837 Standard.

The behaviour and impact of pharmaceuticals in the environment are still poorly understood. Pharmaceuticals are widely used and continually released into the environment causing increasing concerns about their impact on the environment beyond the intended human or veterinary use. Prescribed pharmaceuticals, typically, enter the environment either through excretion after human use or disposal of surplus medication. Sewage treatment plants do not completely remove pharmaceuticals and their metabolites and these have been detected in sewage treatment plant effluent and receiving waters. Land application of treated sewage effluent is widely practiced in New Zealand as an alternative to surface water discharge. Methods were developed to determine selected pharmaceuticals in environmental matrices such as sewage effluent, sewage solids, soil, and soil water. From these, pharmaceutical removal efficiencies were determined for three common sewage treatment processes; activated sludge, composting and land application of sewage effluent. The impacts of some common pharmaceuticals on soil microbial communities, together with the effect of prolonged exposure to sewage effluent on these communities were examined. Additionally, toxicity of sewage effluent, and toxicity mechanisms of specific pharmaceuticals were investigated using luminescent micro-organisms and lettuce seedlings. Pharmaceuticals were successfully detected in sewage effluent, sewage solids, compost, soil and soil water. The sewage treatment processes investigated, including land application, were able to remove or reduce pharmaceutical concentrations in sewage. In case of land application, volcanic soils were more efficient than sandy soils in pharmaceutical removal while irrigation rate and level of sewage pre-treatment also showed some effect on removal efficiency. Pharmaceuticals were not acutely toxic at environmental levels currently detected. Exposure of microbial communities to unnaturally high levels of pharmaceuticals did demonstrate that most pharmaceuticals were potentially able to induce stress in the microbial community although microbes were able to metabolise some of these pharmaceuticals. Twelve years of effluent irrigation resulted in microbial adaptation to aspirin, acetaminophen and tetracycline, indicating that these pharmaceuticals had an effect on microbial community. Presently, land application of treated sewage waste may be a suitable treatment for additional pharmaceutical removal provided that land application schemes are designed appropriately, and pharmaceutical accumulation in the soil is occasionally monitored. It would be prudent to recognise the potential risk that could be caused by chronic exposure to pharmaceuticals such that continued vigilance may lead to future indications of chronic effects at an early stage.

Ο Πατραϊκός Κόλπος βρίσκεται στη Δυτική Ελλάδα μεταξύ Στερεάς Ελλάδας και Πελοποννήσου. Είναι ένας σχετικά αβαθής θαλάσσιος κόλπος που συνδέει το βαθύ Κορινθιακό Κόλπο με το Ιόνιο Πέλαγος. Η περιοχή μελέτης εκτείνεται από την παραλία της Καλόγριας, Δ. Λαρισσού, μέχρι το Ακταίο του Δήμου Ρίου. Πραγματοποιηθήκαν 2 εποχικές δειγματοληψίες, για τη συλλογή θαλάσσιου νερού, μια χειμερινή το Μάρτιο του 2009 και μία θερινή το Σεπτέμβριο του ίδιου έτους. Εμβόλιμα έγινε δειγματοληψία λίγο μετά από ατύχημα πετρελαιοκηλίδας στο λιμάνι της Πάτρας. Στην εργασία αυτή με μία τροποποίηση της μεθόδου MARPOLMON-P, μετρήθηκε η εκπομπή φθορισμού των δειγμάτων μετά από την εκχύλιση τους με εξάνιο και διερευνήθηκε η παρουσία και η συγκέντρωση πετρελαϊκών ενώσεων καθώς και η διασπορά των πετρελαιοειδών στις παράκτιες περιοχές του Πατραϊκού Κόλπου. Σε κάθε δείγμα μετρήθηκαν φυσικές παράμετροι όπως η θερμοκρασία, το pH, η ηλεκτρική αγωγιμότητα και η θολερότητα του θαλάσσιου νερού. Η σύσταση των δειγμάτων της δεύτερης δειγματοληψίας διερευνήθηκε με τη χρήση GC-MS για τον εντοπισμό της πηγής των πετρελαϊκών ρύπων. Τα αποτελέσματα των δύο κύριων δειγματοληψιών παρουσίασαν μεγάλες διακυμάνσεις στη συγκέντρωση αλλά και στην κατανομή των πετρελαϊκών υδρογονανθράκων, με τα εύρη των τιμών των συγκεντρώσεων να κυμαίνονται για τη χειμερινή από 0 – 290 μg/L ισοδύναμων μονάδων χρυσενίου (Λιμάνι Προβλήτα Αγ. Νικολάου) και για τη θερινή δειγματοληψία από 0- 56 μg/L μονάδων χρυσενίου (Μαρίνα Τερψιθέας). Η κατανομή και η διασπορά των πετρελαιοειδών φαίνεται να επηρεάζεται άμεσα από τη διεύθυνση και ταχύτητα των κυμάτων και του επικρατούντος άνεμου στις περιοχές δειγματοληψίας, αλλά και από την ωκεανογραφική συμπεριφορά του Πατραϊκού Κόλπου. Στην ανάλυση GC/MS βρέθηκε μεγάλη αναλογία αλκάνιων σε όλα τα δείγματα, ενώ σε κάποια από αυτά βρέθηκαν πολυκυκλικοί αρωματικοί υδρογονάνθρακες και αλκένια, παράγωγα του πετρελαίου και των καυσίμων. Άλλες οργανικές ενώσεις όπως φθαλικοί εστέρες, σουλφίδια, αλκοόλες κ.α., ανιχνεύτηκαν σε χαμηλές συνήθως συγκεντρώσεις και πιθανόν προέρχονται από ρυπογόνες χερσαίες πηγές (επιφανειακή απορροή, αστικά και βιομηχανικά λύματα κ.α.). / The Gulf of Patras located between Continental Greece and Peloponnesus, in West Greece. The Gulf of Patras is relatively shallow and connects the deep Gulf of Corinth with Ionian Open Sea. The experimental area of our study extends from the beach of Kalogria, department of Municipality of Larissos, to Aktaion, department of Municipality of Rion. Two samplings, one in March of 2009 and one in September of the same year, were carried out in order to get sea water samples. After the occurrence of an oil slick accident in the port of Patras, an interstitial sampling was carried out. In this study, MARPOLMON-P method partially modified was used, in order to estimate the fluorescence emission of the hexane extracted sea water samples. The presence of Dissolved/Dispersed petroleum hydrocarbons (DDPH) was also investigated as well as their concentration and the distribution of those in the maritime areas of the Gulf of Patras. In every sample, physical parameters such as temperature, pH, electrical conductivity and turbidity of sea water were estimated. The identification of various substances within the samples of the second sampling (September of 2009) was conducted with GC-MS method, in order to find out the source of oil pollution. Considering our results of the two main samplings we found out that there were important ranges in concentration as well as in distribution of DDPH. At first sampling the range of values was between 0 to 290 μg/L of chrysene equivalents (Port of St. Nikolaos) and at second sampling was between 0 to 56 μg/L of chrysene equivalents (Port of Marina Terpsithea). The results showed that wave’s direction and speed, wind speed and oceanographical status of Gulf of Patras affected by the distribution and dispersion of petroleum hydrocarbons. During the GC/MS analysis high content of alkanes in all collected samples was identified, while some of them contained polycyclic aromatic hydrocarbons and alkenes, such as products of crude oil and mineral fuel. Other organic compounds such as pthallic esters, sulphides, alcoholes etc were found in low concentrations. These organic compounds were probably derived from pollutant ground sources (superficial rain flow or dilution drainage, urban and manufacturing wastesreams).

O Brasil ocupa posição de destaque no consumo mundial de anfetaminas, contrariamente à tendência mundial de retração. Devido aos efeitos colaterais e ao alto potencial de abuso, a produção e comercialização de anfetaminas vêm sendo controladas no mundo inteiro. Com a restrição de uso, houve um retorno a procura pelos equivalentes naturais, especialmente as efedrinas presentes em diversas especialidades farmacêuticas, utilizadas no tratamento de doenças respiratórias. São componentes de vários compostos emagrecedores, suplementos alimentares e dietéticos utilizados para perda de peso e ganho de massa muscular. Face ao uso indiscriminado e a grande incidência de resultados falso-positivos nos testes de triagem para anfetaminas por imunoensaio enzimático homogêneo, fazem-se necessários testes confirmatórios. Neste sentido, este trabalho se propôs a desenvolver um método confirmatório simples e rápido para detecção, identificação e quantificação de efedrinas (efedrina/pseudoefedrina) em amostras de urina por por cromatografia a gás / espectrometria de massas-massas (CG/EM/EM), passível de ser adotado na rotina de laboratórios de análises toxicológicas. Devido à complexidade da matriz e as peculiaridades do analito, inicialmente procedeu-se o estudo do tratamento da amostra, considerando as etapas de derivatização, extração, pré-concentração e purificação, de modo a fornecer um extrato límpido, livre de impurezas, interferentes e com melhor sensibilidade, linearidade e seletividade analítica. Os métodos de extração usados foram extração líquido-líquido (ELL), extração em fase sólida (SPE) e microextração em fase sólida (SPME). Os resultados indicaram que o reagente de derivatização ciclohexanona foi o que apresentou melhor desempenho, menor custo e promoveu maior seletividade dos diasterômeros EF/PEF em colunas normais de CG. Sendo que o método mais apropriado para a detecção e identificação de efedrinas/anfetamina por CG/EM é a SPME levando em consideração características como simplicidade, rapidez, custo, recuperação e ausência de interferentes. Entretanto, considera-se valido o uso de SPE para a quantificação, devido à possibilidade de pré-concentração do analito. / Brazil is one of the biggest amphetamine consumers in the world, going against the worldwide retraction tendency. Due to serious adverse effects and high abuse potential, the production and commercialization of amphetamines has been controlled around the world. With the restriction of its use, there was a return in the search of natural equivalents, especially the ephedrines found in many medicines utilized in the treatment of respiratory diseases. Furthermore, they are components of dietary supplements used to lose weight and muscular mass gain. Because of the indiscriminate use and the high incidence of false-positive results in the amphetamines screening tests by enzyme immunoassay technique, it is necessary confirmatory tests. In this way, the aim of this work is to develop a confirmatory simple and quickly method for the detection and quantification of ephedrines (ephedrine and pseudoephedrine) gas chromatography / mass-mass spectrometry (GC/MS/MS), with possibility to be adopted in toxicological analyses laboratorial routine. Due to the complexity of the matrix and analyte peculiarities, initially proceeds the study of sample treatment, considering the derivatization, extraction, pre-concentration and purification steps, obtaining a limpidous extract, free of impurities, interferents and with better sensitivity, linearity and analytical selectivity. The extraction method used were liquid-liquid extraction (LLE), solid-phase extraction (SPE) and solid-phase microextraction (SPME). The results indicate that cyclohexanone was the derivatization agent with the best performance, lower price and good selectivity in diasteromers EF/PEF separation in normal GC columns. The most appropriate method for detection and identification of ephedrines/amphetamine by GC/MS is SPME, considering characteristics as simplicity, speed, cost, recovery and absence of interferents. However, the use of SPE must be considered to quantification, since it allowed analyte pre-concentration.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-09-06T16:08:00Z No. of bitstreams: 1 Lopes W A Tese de Doutorado IQ-UFBA 2007.PDF: 2585828 bytes, checksum: 5e4ecce83a58663cda34dce3a68a966c (MD5) / Approved for entry into archive by Vanessa Reis (vanessa.jamile@ufba.br) on 2016-09-08T10:48:19Z (GMT) No. of bitstreams: 1 Lopes W A Tese de Doutorado IQ-UFBA 2007.PDF: 2585828 bytes, checksum: 5e4ecce83a58663cda34dce3a68a966c (MD5) / Made available in DSpace on 2016-09-08T10:48:19Z (GMT). No. of bitstreams: 1 Lopes W A Tese de Doutorado IQ-UFBA 2007.PDF: 2585828 bytes, checksum: 5e4ecce83a58663cda34dce3a68a966c (MD5) / CNPq, FINEP, FAPESB e ANEEL / Os Hidrocarbonetos policíclicos aromáticos (HPA) são poluentes formados geralmente durante a combustão incompleta de petróleo e derivados, carvão mineral, biomassa e outros materiais orgânicos. São emitidos por diversas fontes naturais ou antrópicas e estão presentes na atmosfera, hidrosfera e litosfera. A atmosfera é o seu principal meio de transporte onde se encontram em fase vapor ou adsorvidos em material particulado. Em centros urbanos, sua emissão está associada principalmente aos veículos automotores, movidos a diesel e gasolina. Os HPA e seus derivados, por exemplo, os nitro-HPA e oxi-HPA, são agentes cancerígenos e/ou mutagênicos, daí a importância de estudos sobre a sua presença na atmosfera e em outras matrizes ambientais, sobre a reatividade e atividades biológicas. Neste trabalho, foram determinadas as concentrações atmosféricas para 16 HPA considerados como poluentes prioritários pela agência de proteção ambiental dos Estados Unidos da América (U. S. EPA), em amostras de material particulado atmosférico (MPA), usando o método de CG-EM com monitoramento de íons selecionados. As amostras de MPA foram coletadas em amostradores de grande volume (Hi-vol) e, em seguida, foram extraídas usando a técnica de sonicação e uma solução de acetonitrila e diclorometano (3:1) como solvente. Os extratos foram pré- concentrados (10/1) e em seguida analisados por CG-EM/SIM. Com o objetivo de assegurar uma boa separação dos 16 HPA, no menor tempo de análise, foi utilizado o planejamento multivariado para estabelecer as condições de programação de temperatura do forno (aquecimento da coluna). O processo de otimização foi realizado por meio do planejamento fatorial fracionário e através do planejamento do tipo Box-Behnken, sendo avaliados os seguintes fatores: temperatura inicial (oC), velocidade de elevação da temperatura N° 1 (°C.min-1), temperatura intermediária (oC), velocidade de elevação da temperatura N° 2 (°C.min-1) e temperatura final (oC). As condições otimizadas para a separação dos 16 HPA foram estabelecidas em: 70 °C (2 min) ? 200 °C (30 °C/min, 5 min) ? 300 °C (5 °C/min, 1,67 min). O tempo total da análise, com uma boa separação dos 16 analitos, ficou em 33 minutos. A validação da técnica de CG-EM, no modo SIM, apresentou resultados considerados satisfatórios para a repetitividade da resposta do detector, repetitividade do tempo de retenção, e linearidade das curvas de calibração. Os limites de detecção foram estabelecidos entre 0,13 e 0,34 ng mL-1 (área) e 0,18 e 0,72 ng mL-1 (altura de pico) e os limites de quantificação entre 0,38 e 1,04 ng mL-1 (área) e entre 0,61 e 2,39 ng mL-1 (altura de pico). As amostras ambientais de MPA foram coletadas em quatro diferentes locais, apresentando os seguintes resultados: i) Estação da Lapa (Salvador, BA) - Os HPA presentes em concentrações mais altas foram o criseno (CRI), pireno (PIR) e benzo[b]fluoranteno (BbF), apresentando concentrações médias de respectivamente 2,62, 1,32 e 1,30 ng m-3, e perfil compatível com emissões de veículos movidos a diesel; ii) Porto de Aratu (Candeias, BA) - Os HPA presentes em maiores concentrações foram o benzo[b]fluoranteno (BbF), benzo[g,h,i]perileno (BgP) e Indeno[1,2,3- c,d]pireno (IND), apresentando concentrações médias de respectivamente 2,53, 1,22 e 1,12 ng m-3 (AGV-PTS) e 1,74, 0,82 e 0,73 (AGV MP10); iii) Ilha de Maré, (Salvador, BA) – os valores mais altos foram observados para o benzo[b]fluoranteno (BbF), benzo[b]fluoranteno (BkF) e benzo[g,h,i]perileno (BgP), apresentando concentrações médias de respectivamente 1,62, 0,73 e 0,72 ng m-3; iv) Cidade Universitária da USP (São Paulo, SP) - Os HPA que apresentaram maiores concentrações médias foram o benzo[b]fluoranteno (BbF), criseno (CRI) e o benzo[g,h,i]perileno, com os valores de, respectivamente, 0,93, 0,50 e 0,49 ng m-3. Os resultados foram avaliados em termos de perfil das concentrações, prováveis fontes de emissões e, em alguns casos, por comparação com análises anteriores. / Polycyclic aromatic hydrocarbons (PAH) are ubiquitous pollutants that are emitted from several natural or anthropic sources and may be present in the atmosphere, hydrosphere and lithosphere. They usually originate during the incomplete combustion of petroleum and its derivatives, mineral coal, biomass and other organic materials. They are mainly transported in the atmosphere, being present either in the vapor phase or adsorbed in particulate material. In urban centers, emission is mainly associated with diesel- and gasoline-powered motor vehicles. Since PAH and derivatives, e.g. nitro-PAH and oxy-PAH, are carcinogenic and/or mutagenic agents, to study the effect of their presence in the atmosphere and in other environmental matrices on the biological activity and reactivity are of key relevance. In this study, the atmospheric concentrations of the 16 PAHs that are considered priority pollutants by the U.S. Environmental Protection Agency were evaluated in samples of atmospheric particulate material (APM), using gas chromatography / mass spectrometry with selected-ion monitoring mode (GC-MS/SIM). APM samples were collected in high-volume air samplers (Hi-vol) and then extracted under sonication with a solution of acetonitrile and dichloromethane (3:1) as a solvent. Extracts were pre-concentrated (10/1) and analyzed by GC-MS/SIM. In order to assure an adequate separation of the 16 PAHs, in the shortest analysis time, a multivariate design was used to set the conditions of the oven temperature program (column warming). The optimization process was carried out using factorial fractional design and Box-Behnken design. The following factors were evaluated: initial temperature (ºC), temperature rate N°1 (ºC.min-1), intermediate temperature (ºC), temperature rate N°2 (ºC.min-1) and final temperature (ºC). The optimized conditions for the separation of the 16 PAH were set at: 70 ºC (2 min) → 200 ºC (30 ºC/min, 5 min) → 300 ºC (5 ºC/min, 1.67 min). Total analysis time, with an adequate separation of the 16 analytes was 33 minutes. Validation of GC-MS in the SIM mode rendered satisfactory results for repeatability of detector response, repeatability of retention time, and linearity of calibration curves. Detection limits were established between 0.13 and 0.34 ng mL- 1 (area) and 0.18 and 0.72 ng mL-1 (peak height). Environmental samples of PMA were collected at four different locations, with the following results: i) Lapa Bus Station (Salvador, BA) - The PAH with the highest concentrations were crysene (CRY), pyrene (PYR) and benzo[b]fluoranthene (BbF), with mean concentrations of 2.62, 1.32, and 1.30 ng m-3, respectively, suggesting a profile compatible with diesel vehicle emissions; ii) Port of Aratu (Candeias, BA) – The PAH with the highest concentrations were benzo[b]fluoranthene (BbF), benzo[g,h,i]perylene (BgP) and indeno[1,2,3-c,d]pyrene (IND), with mean concentrations of 2.53, 1.22, and 1.12 ng m-3 (TSP) and 1.74, 0.82 e 0.73 (PM10), respectively; iii) Ilha de Maré, (Salvador, BA) – The PAH with the highest concentrations were benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF) and benzo[g,h,i]perylene (BgP), with mean concentrations of 1.62, 0.73 e 0.72 ng m-3, respectively; iv) University of São Paulo (São Paulo, SP) - The PAH with the highest mean concentrations were benzo[b]fluoranthene (BbF), chrysene (CRI) and benzo[g,h,i]perylene (BgP) with values of 0.93, 0.50 and 0.49 ng m-3, respectively. The results were evaluated with respect to concentration profile, probable emission sources and in some cases, were compared to prior analyses.

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2014-09-19T18:04:41Z No. of bitstreams: 1 Tese_Sarah_Rocha_LSGT.pdf: 3229640 bytes, checksum: af1acce9c5d43271ea20530b0fd1f510 (MD5) / Approved for entry into archive by Fatima Cleômenis Botelho Maria (botelho@ufba.br) on 2014-09-22T12:43:20Z (GMT) No. of bitstreams: 1 Tese_Sarah_Rocha_LSGT.pdf: 3229640 bytes, checksum: af1acce9c5d43271ea20530b0fd1f510 (MD5) / Made available in DSpace on 2014-09-22T12:43:20Z (GMT). No. of bitstreams: 1 Tese_Sarah_Rocha_LSGT.pdf: 3229640 bytes, checksum: af1acce9c5d43271ea20530b0fd1f510 (MD5) / Um método de extração em ponto nuvem de hidrocarbonetos policíclicos aromáticos foi desenvolvido, utilizando tensoativos octilfenol polietoxilados com derivatização do coacervato, como etapa que antecede a detecção por cromatografia a gás acoplada à espectrometria de massa. Foi realizado um estudo da influência da presença de aditivos na redução da temperatura de ponto nuvem do OPEO30 e do OPEO35, surfactantes com temperaturas de ponto nuvem superiores a 100 oC, através adição de sais, álcoois, OPEO7.5 e misturas de sais e álcoois. Observou-se em todos os casos diminuição da temperatura, sendo o sulfato de sódio o aditivo que resultou maior redução da temperatura. Selecionou-se o OPEO30 para as demais etapas do trabalho. Fez-se a otimização das condições da reação de derivatização do coacervato por meio de planejamento fatorial 23, utilizando-se a resposta global para avaliar os resultados. Selecionou-se as condições do ponto central do planejamento fatorial, ou seja, 125 L de BSTFA, 100 L de piridina e banho de água à 70 oC por 45 min, para a derivatização de 30 L de fase rica em surfactante. O procedimento de ponto nuvem foi otimizado, sendo avaliadas as variáveis concentração de surfactante, temperatura e tempo de banho de água, sendo proposta a seguinte metodologia: 1,0 mL de OPEO30 10% m v-1, 10,0 mL de amostra, 1,25 g de sulfato de sódio anidro, banho de água à 70 oC por 10 min, centrifugação à 3000 rpm por cinco min. O método mostrou-se seletivo, sendo observado efeito de matriz intenso, o qual foi corrigido. Os limites de quantificação obtidos estão entre 39 e 176 ng L-1. O método proposto também foi comparado com o método USEPA 3510C, estando as concentrações obtidas, quando analisada uma amostra real de água subterrânea, bem próximas, com recuperações variando entre 90,0 e 97,5 %. O método proposto foi aplicado a amostras de água subterrânea coletadas em poços localizados em postos de revenda de combustíveis. Em todas as amostras foram detectados HPA. / A method for cloud point extraction of polycyclic aromatic hydrocarbons was developed using surfactants octylphenol polyethoxylated with the coacervate derivatization as step prior to gas chromatography-mass spectrometry detection. An influence of additives study on the reduction of cloud point temperature OPEO30 and OPEO35, surfactants with cloud point temperatures above 100 ° C, was conducted, by addition of salts, alcohols, and mixtures OPEO7.5 salts and alcohols. It was observed in all cases cloud point reduction and sodium sulfate was the additive that result in a most effective. The OPEO30 was selected for others work steps. The factorial design 23 was used to optimize the reaction of derivatization, using the global response to evaluate the results. Were selected the central point experimental design condition, 125 L of BSTFA, 100 L of pyridine and water bath at 70 oC for 45 min for 30 L of surfactant-rich phase derivatization. The cloud point extraction procedure was optimized and surfactant concentration, heating bath temperature and time variables, were evaluated. Was proposed the following method: 1,0 mL of OPEO30 10% v m-1 solution, 10,0 mL of sample, 1,25 g of anhydrous sodium sulfate, water bath at 70 °C for 10 min. The centrifugation was performed at 3000 rpm for five min, removing the aqueous layer after each centrifugation step. A 30L coacervate aliquot was withdrawn, and performed derivatization and subsequent GC-MS analysis. The method was validated. The method was selective, an intense matrix effect was observed and was corrected. The quantification limits obtained were between 39 and 176 ng L-1.

O Brasil ocupa posição de destaque no consumo mundial de anfetaminas, contrariamente à tendência mundial de retração. Devido aos efeitos colaterais e ao alto potencial de abuso, a produção e comercialização de anfetaminas vêm sendo controladas no mundo inteiro. Com a restrição de uso, houve um retorno a procura pelos equivalentes naturais, especialmente as efedrinas presentes em diversas especialidades farmacêuticas, utilizadas no tratamento de doenças respiratórias. São componentes de vários compostos emagrecedores, suplementos alimentares e dietéticos utilizados para perda de peso e ganho de massa muscular. Face ao uso indiscriminado e a grande incidência de resultados falso-positivos nos testes de triagem para anfetaminas por imunoensaio enzimático homogêneo, fazem-se necessários testes confirmatórios. Neste sentido, este trabalho se propôs a desenvolver um método confirmatório simples e rápido para detecção, identificação e quantificação de efedrinas (efedrina/pseudoefedrina) em amostras de urina por por cromatografia a gás / espectrometria de massas-massas (CG/EM/EM), passível de ser adotado na rotina de laboratórios de análises toxicológicas. Devido à complexidade da matriz e as peculiaridades do analito, inicialmente procedeu-se o estudo do tratamento da amostra, considerando as etapas de derivatização, extração, pré-concentração e purificação, de modo a fornecer um extrato límpido, livre de impurezas, interferentes e com melhor sensibilidade, linearidade e seletividade analítica. Os métodos de extração usados foram extração líquido-líquido (ELL), extração em fase sólida (SPE) e microextração em fase sólida (SPME). Os resultados indicaram que o reagente de derivatização ciclohexanona foi o que apresentou melhor desempenho, menor custo e promoveu maior seletividade dos diasterômeros EF/PEF em colunas normais de CG. Sendo que o método mais apropriado para a detecção e identificação de efedrinas/anfetamina por CG/EM é a SPME levando em consideração características como simplicidade, rapidez, custo, recuperação e ausência de interferentes. Entretanto, considera-se valido o uso de SPE para a quantificação, devido à possibilidade de pré-concentração do analito. / Brazil is one of the biggest amphetamine consumers in the world, going against the worldwide retraction tendency. Due to serious adverse effects and high abuse potential, the production and commercialization of amphetamines has been controlled around the world. With the restriction of its use, there was a return in the search of natural equivalents, especially the ephedrines found in many medicines utilized in the treatment of respiratory diseases. Furthermore, they are components of dietary supplements used to lose weight and muscular mass gain. Because of the indiscriminate use and the high incidence of false-positive results in the amphetamines screening tests by enzyme immunoassay technique, it is necessary confirmatory tests. In this way, the aim of this work is to develop a confirmatory simple and quickly method for the detection and quantification of ephedrines (ephedrine and pseudoephedrine) gas chromatography / mass-mass spectrometry (GC/MS/MS), with possibility to be adopted in toxicological analyses laboratorial routine. Due to the complexity of the matrix and analyte peculiarities, initially proceeds the study of sample treatment, considering the derivatization, extraction, pre-concentration and purification steps, obtaining a limpidous extract, free of impurities, interferents and with better sensitivity, linearity and analytical selectivity. The extraction method used were liquid-liquid extraction (LLE), solid-phase extraction (SPE) and solid-phase microextraction (SPME). The results indicate that cyclohexanone was the derivatization agent with the best performance, lower price and good selectivity in diasteromers EF/PEF separation in normal GC columns. The most appropriate method for detection and identification of ephedrines/amphetamine by GC/MS is SPME, considering characteristics as simplicity, speed, cost, recovery and absence of interferents. However, the use of SPE must be considered to quantification, since it allowed analyte pre-concentration.

O Brasil ocupa posição de destaque no consumo mundial de anfetaminas, contrariamente à tendência mundial de retração. Devido aos efeitos colaterais e ao alto potencial de abuso, a produção e comercialização de anfetaminas vêm sendo controladas no mundo inteiro. Com a restrição de uso, houve um retorno a procura pelos equivalentes naturais, especialmente as efedrinas presentes em diversas especialidades farmacêuticas, utilizadas no tratamento de doenças respiratórias. São componentes de vários compostos emagrecedores, suplementos alimentares e dietéticos utilizados para perda de peso e ganho de massa muscular. Face ao uso indiscriminado e a grande incidência de resultados falso-positivos nos testes de triagem para anfetaminas por imunoensaio enzimático homogêneo, fazem-se necessários testes confirmatórios. Neste sentido, este trabalho se propôs a desenvolver um método confirmatório simples e rápido para detecção, identificação e quantificação de efedrinas (efedrina/pseudoefedrina) em amostras de urina por por cromatografia a gás / espectrometria de massas-massas (CG/EM/EM), passível de ser adotado na rotina de laboratórios de análises toxicológicas. Devido à complexidade da matriz e as peculiaridades do analito, inicialmente procedeu-se o estudo do tratamento da amostra, considerando as etapas de derivatização, extração, pré-concentração e purificação, de modo a fornecer um extrato límpido, livre de impurezas, interferentes e com melhor sensibilidade, linearidade e seletividade analítica. Os métodos de extração usados foram extração líquido-líquido (ELL), extração em fase sólida (SPE) e microextração em fase sólida (SPME). Os resultados indicaram que o reagente de derivatização ciclohexanona foi o que apresentou melhor desempenho, menor custo e promoveu maior seletividade dos diasterômeros EF/PEF em colunas normais de CG. Sendo que o método mais apropriado para a detecção e identificação de efedrinas/anfetamina por CG/EM é a SPME levando em consideração características como simplicidade, rapidez, custo, recuperação e ausência de interferentes. Entretanto, considera-se valido o uso de SPE para a quantificação, devido à possibilidade de pré-concentração do analito. / Brazil is one of the biggest amphetamine consumers in the world, going against the worldwide retraction tendency. Due to serious adverse effects and high abuse potential, the production and commercialization of amphetamines has been controlled around the world. With the restriction of its use, there was a return in the search of natural equivalents, especially the ephedrines found in many medicines utilized in the treatment of respiratory diseases. Furthermore, they are components of dietary supplements used to lose weight and muscular mass gain. Because of the indiscriminate use and the high incidence of false-positive results in the amphetamines screening tests by enzyme immunoassay technique, it is necessary confirmatory tests. In this way, the aim of this work is to develop a confirmatory simple and quickly method for the detection and quantification of ephedrines (ephedrine and pseudoephedrine) gas chromatography / mass-mass spectrometry (GC/MS/MS), with possibility to be adopted in toxicological analyses laboratorial routine. Due to the complexity of the matrix and analyte peculiarities, initially proceeds the study of sample treatment, considering the derivatization, extraction, pre-concentration and purification steps, obtaining a limpidous extract, free of impurities, interferents and with better sensitivity, linearity and analytical selectivity. The extraction method used were liquid-liquid extraction (LLE), solid-phase extraction (SPE) and solid-phase microextraction (SPME). The results indicate that cyclohexanone was the derivatization agent with the best performance, lower price and good selectivity in diasteromers EF/PEF separation in normal GC columns. The most appropriate method for detection and identification of ephedrines/amphetamine by GC/MS is SPME, considering characteristics as simplicity, speed, cost, recovery and absence of interferents. However, the use of SPE must be considered to quantification, since it allowed analyte pre-concentration.

This paper reports the study of composition and variation of the chemical components of essential oils of Croton species of Sergipe emphasizing its importance chemotaxonomy. Essential oils from fresh aerial parts obtnained by hydrodistillation from samples of Croton blanchetianus (CB-GA), C. campestris (CC-AML), C. heliotropiifolius collected at different locations in the Sergipe (CH-SG1, CH-SG2, CH-GA, and CH-AML), C. pedicellatus (CP-SI), C. tetradenius (CT-SG) and seven other unidentified taxa, called CSP1-CPS7, were analyzed by GC-MS and GC-FID, such analysis revealed a highly variable chemical composition. It were identified 131 components by comparing the retention indices and mass spectra of compounds with literature data and NIST and Willey mass spectra libraries. With the chemical analysis of oil of Croton were established correlations between the taxa of C. heliotropiifolius, which can be differentiated by using their main chemical markers: (E)-caryophyllene and bicyclogermacrene. For comparative analysis of the chemical composition of essential oils of Croton species, chemometric tools as Principal Component Analysis (PCA) and hierarchic Cluster Analysis (HCA) was applied, by which it was possible to differentiate the components of the essential oil of aerial parts of Croton species grouped by class of compounds according to their biosynthetic origin (monoterpene hydrocarbons, oxygenated monoterpenes, sesquiterpene hydrocarbons, oxygenated sesquiterpenes, phenylpropanoids and derivatives of fatty acids). With this analysis it was possible to form three groups (I, II and III), corroborating the comparative analysis of chromatographic profiles. To our knowledge, this is the first report on the chemical composition of essential oils of C. pedicellatus and C. tetradenius. / Este trabalho relata o estudo da composição e variação dos componentes químicos do óleo essencial das espécies de Croton do estado de Sergipe dando ênfase a sua importância quimiotaxonômica. Os óleos essenciais das partes aéreas frescas obtidos por hidrodestilação das amostras de Croton blanchetianus (CB-GA), C. campestris (CC-AML), C. heliotropiifolius coletadas em diferentes localidades do Estado (CH-SG1, CH-SG2, CH-GA, CH-SI e CH-AML), C. pedicellatus (CP-SI), C. tetradenius (CT-SG) e outros sete táxons ainda não identificados denominados (CSP1-CPS7) foram analisados por CG-EM e CG-DIC revelando uma composição química bastante variável. Foram identificados 131 componentes, baseados nos índices de retenção e na comparação de seus espectros de massas com os da literatura e com as bibliotecas de espectros de massas Willey e NIST. Com a análise química dos óleos de Croton foram estabelecidas correlações entre os táxons de C. heliotropiifolius, os quais foram diferenciados dos demais mediante a utilização de seus marcadores químicos principais: (E)-cariofileno e biciclogermacreno. Para as análises comparativas da composição química dos óleos essenciais das espécies de Croton aplicaram-se ferramentas quimiométricas de Análise dos Componentes Principais (ACP) e Análise de Agrupamentos Herarquicos (AAH), pelas quais foi possível diferenciar os componentes do óleo essencial das partes aéreas das espécies de Croton agrupados por classe de compostos de acordo com sua origem biossintética (hidrocarbonetos monoterpênicos, monoterpenos oxigenados, hidrocarbonetos sesquiterpênicos, sesquiterpenos oxigenados, fenilpropanóides e derivados de ácidos graxos). Com essas análises foi possível a formação de três grupos (I, II e III), corroborando com as análises comparativas dos perfis cromatográficos. Ao nosso conhecimento, este é o primeiro relato sobre a composição química dos óleos essenciais de C. pedicellatus e C. tetradenius.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The mangrove plays an important role for the man since prehistoric times because of the abundance of food resources it provides, in addition to being a natural breeding that serves as a shelter for several species of animals, including uçá-crab, which is great importance for the maintenance of this ecosystem. However, this environment is the final destination of many pollutants, including polycyclic aromatic hydrocarbons (PAH). The aim of this work is to develop and validate a method using the extraction technique for matrix solid-phase dispersion (MSPD) and gas chromatography coupled with mass spectrometry (GC/MS) for the determination of priority PAH in hepatopancreas of uçá-crab (Ucides cordatus). The best extraction conditions were obtained using 0.5 g hepatopancreas, 1.5 g florisil as a dispersant and 0.5 g sodium sulfate as the drying agent, along with 0.5 g of C18 as an auxiliary adsorbent, and eluting with 10 mL of acetonitrile. The analytical validation was performed from the parameters: selectivity; linearity, which was estimated from the correlation coefficient, with values greater than 0.990 for all PAH in a concentration range of 5 ng mL-1 to 100 ng mL-1; limits of detection and quantification in the intervals of 0.2 to 3.0 ng g-1 and 0.6 to 9,8 ng g-1 respectively; accuracy and precision, with recovery values between 60-111% and coefficients of variation in the 1-19% range for concentration levels of 10, 25 and 50 ng mL-1; and robustness, which was assessed by external standard, being robust for most of the HPA tested, with the exception of naphthalene. For the application of validated method were collected uçá-crab from mangroves located in the Gameleiro rivers (P1), Vaza-Barris (P2), Poxim (P3) and Sergipe (P4). At point P3 found a concentration of 26.6 ng g -1 of benzo[a]anthracene , which is considered as "probably carcinogenic". Mangrove sediments were also collected the same points and extracted by a method already validated, which is based on ultrasound extraction, and analyzed by GC/MS. The concentration values found for ΣPAH ranged from 12.5 to 813.6 ng g-1 of dry sediment. / O manguezal tem um papel importante para o homem desde a pré-história em razão da abundância de recursos alimentares que fornece, além de constituir um criadouro natural que serve de abrigo para diversas espécies de animais, entre eles o caranguejo-uçá, que é de grande importância para a manutenção desse ecossistema. Contudo, esse ambiente é destino final de muitos contaminantes, entre eles os hidrocarbonetos policíclicos aromáticos (HPA). O objetivo desse trabalho é desenvolver e validar um método, utilizando a técnica de extração por dispersão da matriz em fase sólida (MSPD) e cromatografia gasosa acoplada a espectrometria de massas (GC/MS), para a determinação de HPA prioritários em hepatopâncreas do caranguejo-uçá (Ucides cordatus). As melhores condições de extração foram obtidas utilizando 0,5 g do hepatopâncreas, 1,5 g de florisil como dispersante e 0,5 g de sulfato de sódio como agente secante, juntamente com 0,5 g de C18 como adsorvente auxiliar e eluição com 10 mL de acetonitrila. A validação analítica foi realizada através da obtenção dos parâmetros de: seletividade; linearidade, que foi estimada a partir do coeficiente de correlação, apresentando valores maiores do que 0,990 para todos os HPA, numa faixa de concentração de 5 ng mL-1 a 100 ng mL-1 ; limites de detecção e quantificação, nos intervalos de 0,2 a 3,0 ng g-1 e 0,6 a 9,8 ng g-1 respectivamente; exatidão e precisão, com valores de recuperação variando entre 60-111% e coeficientes de variação na faixa de 1-19%, para níveis de concentração 10, 25 e 50 ng mL-1; e robustez, que foi avaliada por padronização externa, mostrando-se robusto para a maioria dos HPA testados, com exceção do naftaleno. Para a aplicação do método validado foram coletados caranguejos-uçá de mangues localizados nos rios Gameleiro (P1), Vaza-Barris (P2), Poxim (P3) e Sergipe (P4). No ponto P3 foi encontrada uma concentração de 26,6 ng g-1 do benzo[a]antraceno, que é considerado como “provavelmente cancerígeno” ao homem. Os sedimentos de mangue também foram coletados nos mesmos pontos e extraídos por um método já validado, no qual se baseia na extração por ultrassom, e analisados por GC/MS. Os valores de concentração encontrados para o ΣHPA variaram entre 12,5 – 813,6 ng g-1 de sedimento seco.