O uso de técnicas miniaturizadas de preparo de amostra vem se tornando uma tendência cada vez mais crescente em química analítica. Dentre elas o MEPS (Microextraction by a Packed Sorbent) apresenta grande potencial por poder ser acoplado on-line, sem grandes modificações, à cromatografia gasosa e líquida, não necessitando de grande quantidade de tempo para análise e seu cartucho sorvente ser reutilizável. O uso de MEPS, foi mais explorado até o presente momento na análise de fármacos em fluídos biológicos; dessa forma existe um pequeno número de publicações que exploram o uso dessa técnica na determinação de agrotóxicos em matrizes de alimentos. Por esse motivo, o presente trabalho teve como objetivo a avaliação do uso dessa técnica na determinação de seis agrotóxicos utilizados no cultivo da cana-de-açúcar (tebutiurom, carbofurano, atrazina, metribuzim, ametrina e bifentrina) em amostras de garapa. Para o desenvolvimento desse estudo foram verificadas dentre as variáveis pH, força iônica, solvente de eluição e volume do solvente de eluição, quais poderiam afetar o desempenho da técnica em diferentes fases extratoras, empregando nessa etapa de otimização planejamento fatorial fracionário 24-1. As fases avaliadas foram C18 Chromabond e HLB Oasis, assim como sistemas comercialmente disponíveis com as fases C18, C8, SAX, SCX e SIL. Durante essa etapa foi realizado um estudo inicial do uso do grafeno como material sorvente em MEPS, considerando as propriedades que esse material apresenta para atuar como adsorvente em técnicas de preparo de amostra. Contudo, o uso do grafeno apresentou entupimento no cartucho de sorção, problema ainda em avaliação. A fase C18 Chromabond foi a que apresentou os melhores resultados, sendo a escolhida para otimização dos parâmetros envolvidos na etapa de extração por MEPS. Os parâmetros otimizados por planejamento fatorial 23 foram os ciclos de: aspiração da amostra, lavagem e eluição. O método desenvolvido foi validado baseado nos critérios exigidos pelo MAPA e apresentou seletividade, linearidade e os limites de quantificação variaram de 2-10 μg/L. A recuperação foi adequada para todos os analitos (71,7-106,9%), assim como a precisão intra e inter-dia que apresentou coeficientes de variação (CV) menores que 16%. O método desenvolvido foi aplicado em quatro amostras reais de garapa de diferentes regiões. / The use of miniaturized techniques in sample preparation has becoming a growing trend in analytical chemistry. Among these techniques MEPS (Microextraction by a Packed Sorbent) presents a great potential affording on-line coupling, without much modification to gas and liquid chromatography systems, in addition it does not require large analyses time and the sorbent cartridge is reusable. MEPS utilization has been explored mainly for drugs analyses in biological fluids, existing limited number of publications that apply this technique for pesticides analyses in food sample matrix. For this reason the goal of present work was the evaluation of MEPS in the analyses of six pesticides used in sugarcane cultivation (tebuthiuron, carbofuran, atrazine, metribuzine, ametryn and bifenthrin) in sugarcane juice samples. During the method development several variables were evaluated including pH, ionic strength, elution solvent and solvent volume, to determine which ones could affect the technique perform in different sorbent phases. For this optimization step, fractional factorial design 24-1 was utilized. Phases evaluated included C18 Chromabond and HLB Oasis, and also commercially available system containg C18, C8, SAX, SCX e SIL. During this step, it was also carried out an initial study employing graphene in a MEPS system; Tanking into account the properties that this material presents to act as adsorbent in sample preparation techniques. However the graphene showed obstruction problems in the sorption cartridge, whose solution is under way. The phase C18 Chromabond showed better results, and was chosen to MEPS parameters optimization. MEPs parameters optimized by full factorial desing 23 were the following cycles: sample aspiration, washing and elution. The method, was validated based upon the MAPA requirements and showed good selectivity, linearity an quantifications limits ranging from 2-10 μg/L. Recovery was satisfactory for all pesticides (71,7-106,9%), intra- and inter-day precision were satisfactory and showed coefficients of variation (CV) less than 16%. Hence, the developed method was applied to the analysis of four real samples of sugarcane juice obtained from different regions.

O estado de São Paulo é responsável por 70% da produção nacional de flores e plantas ornamentais. Esses cultivos ocupam 7,5 mil hectares e mais da metade desta área é cultivada em estufas. Atualmente existem aproximadamente 8 mil produtores de pequeno, médio e grande porte em todo Brasil e este setor gera em torno de 200 mil empregos diretos, abrangendo produção e comércio. As estufas são microcosmos planejados para propiciar as condições ambientais adequadas ao crescimento de plantas. Qualquer infestação é controlada usando praguicidas que, devido ao enclausuramento e ajustes das condições climáticas, podem prolongar e intensificar a exposição ocupacional aos mesmos. Alguns estudos sugerem que os trabalhadores de estufas de flores e plantas ornamentais estão expostos a níveis mais elevados de praguicidas durante o carregamento, mistura e aplicação dos praguicidas, bem como pelo contato contínuo com as flores e plantas ornamentais, quando comparados a outros trabalhadores que entram em contato com essa classe de compostos. No presente trabalho, objetivou-se conhecer o processo de trabalho, práticas de saúde, higiene e segurança e localizar possíveis fontes de exposição ocupacional a praguicidas nas estufas de flores da região do Alto Tietê, e também otimizar métodos analíticos para a detecção e quantificação de praguicidas organofosforados (diclorvós, metil-paration e metidation) em patches de algodão e em tubos coletores XAD-2, com o intuito de analisar a exposição ocupacional dérmica e inalatória. O processo de avaliação incluiu o acompanhamento da jornada de trabalho, entrevistas e aplicação de questionários de trabalhadores de 18 estufas. Destas 18 foram selecionadas 6 estufas para coleta de amostras. Os organofosforados diclorvós, metidation e metilparation foram detectados e quantificados por cromatografia gasosa/espectrometria de massas (GC-MS), operado no modo de ionização por impacto de elétrons. Os dados da avaliação qualitativa demonstraram percentual elevado de desconhecimento das práticas adequadas de saúde, higiene e segurança para a utilização destes compostos, sugerindo que há risco de exposição durante a manipulação, armazenamento e descarte dos mesmos. Os limites de quantificação (LQ) obtidos foram abaixo de 0,4 ng/mL e limites de detecção (LD) foram abaixo de 0,1 ng/mL para todos os compostos. O método mostrou boa linearidade na concentração estudada (LSQ-500 ng/mL), com coeficiente (r) maior que 0,99. A precisão foi avaliada pelo desvio padrão relativo e apresentou valores inferiores a 15% para todos os compostos estudados. Após os métodos serem validados, foi realizada a amostragem dérmica e do ar e encontraram-se concentrações variadas de praguicidas. / The state of São Paulo - Brazil, accounts for 70% of domestic production of flowers and ornamental plants. Currently, these crops occupy 7.5 thousand hectares and over 50% of this area is cultivated in greenhouses. This market has an average of 8.000 producers and generates around 200.000 jobs. Greenhouses are microcosms designed to provide environmental conditions suitable for plant growth. Infestation is controlled using pesticides that due to the closure and adjustment to the weather conditions can prolong and intensify the exposure to them. Some studies suggest that workers in greenhouses of flowers and ornamental plants are exposed to higher levels of pesticides during loading, dilution and application, as well as by continuous contact with flowers and ornamental plants, when compared to other workers who enter in contact with this class of compounds. The aim of the present was to know the work process, to survey the practices of health, hygiene and safety standards and locate possible sources of occupational exposure to pesticides in greenhouses of flowers in the Alto Tietê region (São Paulo state), and to optimize analytical methods for detection and quantification of organophosphate pesticides (dichlorvos, methyl parathion and methidathion) in patches of cotton and in XAD-2 sorbent tubes, with the aim of analyzing the occupational dermal and inhalation exposure. The evaluation process included the monitoring of the working day, interviews and questionnaires, and samples collected in greenhouses. The organophosphorus compounds were detected and quantified by gas chromatography/mass spectrometry (GC-MS) operated in electron impact ionization. The data show a high percentage of lack of appropriate health practices, hygiene and safety for pesticide use suggests that there is risk of exposure during handling, storage and disposal of them. The limits of quantification (LOQ) obtained were below 0.4 ng/mL and limits of detection (LOD) were below 0.1 ng/mL for all compounds. The method showed good linearity in the studied concentration (LOQ-500 ng/mL), with coefficient (r) greater than 0.99. The precision was evaluated by relative standard deviation and showed values below 15% for all compounds studied. After the methods are validated, the dermal and air sampling was performed and a great range of pesticide concentrations was found. So it is evident that this study is valuable for future analysis and guidance to workers about possible hazards and proper use for reducing exposure to these compounds.

Estima-se atualmente que mais de 5% da população mundial vem fazendo uso recreativo de algum tipo de substância psicoativa, sendo que o direito a esse uso é tema recorrente da sociedade contemporânea. Por apresentar riscos associados à saúde e a segurança das populações, o uso abusivo dessas substâncias tem instigado a toxicologia social na busca de respostas, com as quais se possa caracterizar, analisar e gerenciar esses riscos. Drogas de grande consumo no Brasil são a anfetamina, cocaína e Cannabis sativa. Esta tese desenvolveu uma nova metodologia para detectar e quantificar anfetamina, cocaína e tetrahidrocanabinol em sangue total, com uso de microextração em fase líquida via fibra de polipropileno (HF-LPME), seguida de cromatografia gasosa acoplada a espectrometria de massa (GC-MS). Trata-se de uma técnica que apresenta vantagens sobre as tradicionais, uma vez que demanda quantidades menores de solvente orgânico, diminuindo riscos e custos de processo. Também propôs um estudo com a aplicação dos métodos em 69 amostras de sangue de vivos e de post mortem, as quais foram obtidas por convênio com a superintendência da polícia técnica científica de São Paulo (SPTC/SP). Os métodos desenvolvidos foram validados de acordo com diretrizes internacionais de interesse forense. Como resultado da validação, os métodos desenvolvidos se mostraram precisos e exatos para anfetamina e cocaína. O limite de detecção da cocaína foi de 5 ng . mL-1 e o limite de quantificação de 10 ng . mL-1. Quanto a anfetamina, os limites de detecção e de quantificação foram de 5 ng . mL-1. A técnica de HF-LPME não foi aplicável ao tetraidrocanabinol (Δ9-THC). Como resultado da análise das amostras, 40% delas apresentaram resultados positivos para cocaína. Desses positivos, 35% foram oriundos das matrizes de sangue de vivos e 64% oriundos de sangue post mortem. Nenhuma delas apresentou resultado quantificável para anfetamina. / It is currently estimated that more than 5% of the world\'s population has been doing recreational use of some kind of psychoactive substances and the legal right to such use is a recurring theme debated by contemporary society. Due to the risks associated with populations health and safety, the abusive use of these substances has been instigating by social toxicology to search for answers to characterize, analyze and manage these risks. Drugs of great consumption in Brazil are, amphetamine cocaine and marijuana. This thesis proposes to develop a new methodology to detect and quantify psychoactive drugs in whole blood with the use of liquid phase microextraction by polypropylene fiber (HFLPME), followed by gas chromatography coupled to mass spectrometry (GC-MS). It is a technique that presents advantages compared with traditional ones, because of the smaller amounts demands of organic solvent, reducing risks and process costs. It also proposes a study with 69 blood samples taken from living persons and post mortem blood samples, which were obtained by agreement with the Superintendency of São Paulo Scientific Technical Police (SPTC / SP). The methods developed were validated according to international guidelines of forensic interest. As a result of the validation, the methods developed were precise and accurate for amphetamine and cocaine. The limit of cocaine detection was 5 ng . mL-1 and the limit of quantification was 10 ng . mL-1. As for amphetamine, the limits of detection and quantification were 5 ng . mL-1. The HF-LPME technique was not applicable to tetrahydrocannabinol (Δ9-THC). As a result of the sample analysis, 40% of them presented positive results for cocaine. Of these, 35% were from blood samples taken from living persons and 64% from the post mortem blood samples. None of the samples presented quantifiable results for amphetamine.

Malgré une sensible baisse des ventes depuis quelques années, la France reste le premier utilisateur européen de phytosanitaires. Ceci n’est pas sans conséquences sur l’environnement et les organismes non visés par ces produits. De nombreuses études ont permis d’une part de mieux comprendre les phénomènes de transfert des pesticides dans les compartiments eau-air sols et d’autre part de mettre en évidence leur contamination. Les données concernant l’eau sont plus nombreuses du fait de son statut de réceptacle ultime des pollutions.et des normes établies par les textes réglementaires. La Directive Cadre européenne sur l’Eau (DCE) adoptée en 2000 vise à atteindre le bon état chimique et écologique des eaux d’ici 2015 avec une obligation de résultats. Le bon état chimique dépend du respect des normes de qualité environnementales (NQE) établies notamment pour 24 pesticides. En 2012, 5% des points de mesure en cours d’eau et 19% des points de mesure en eaux souterraines ne respectent pas ces NQE.Le Languedoc Roussillon est depuis de nombreuses années la première région viticole de France et souffre d’une pression phytosanitaire importante. En 2014, un rapport de l’Agence Régionale de Santé (ARS) fait même état de l’utilisation encore récente de pesticides interdits (simazine, terbuthylazine…) depuis le début des années 2000. L’ARS a de plus affirmé que la plupart des cas de non-conformité avérés pouvaient être rattachés à la présence d’activité agricole dans le bassin versant du captage.Remédier à ces contaminations passe par le suivi de la qualité des eaux et la caractérisation de la pollution. Les outils actuels s’avèrent ne pas être toujours représentatifs de cette pollution ;de nouveaux outils sont donc mis au point. L’étude présentée ici porte sur l’utilisation de l’échantillonnage passif de type POCIS (Polar Organic Chemical Integrative Sampler) pour le suivi de la contamination en pesticides de trois bassins versants languedociens : Paulhan,Puissalicon, Roujan.Dans un premier temps, l’étude des limites possibles du dispositif POCIS a été faite pour évaluer son applicabilité dans les conditions d’exposition imposées par le terrain. Le comportement des molécules au sein de l’outil a été étudié pour une meilleure compréhension des phénomènes de diffusion qui s’y produisent. Ces études ont mené à la mise en place de calibrations en laboratoire en conditions contrôlées. [...] La mise en place des dispositifs POCIS sur les trois sites d’études a mis en évidence la prédominance de pesticides utilisés en viticulture et a montré tout l’intérêt de l’outil d’un point de vue qualitatif. La comparaison de l’outil avec l’échantillonnage automatisé montre des disparités entre concentration réelle et concentration estimée via le POCIS. Ce dernier reste à améliorer d’un point de vue quantitatif pour obtenir un échantillonneur fiable et robuste pour ce type de milieu d’exposition. / Despite a noticeable sales decrease since few years, France remains the first european user of phytosanitary products. This is not without consequences on the environment and the untargeted organisms. Several studies allowed on one hand to better understand phenomena of pesticides transfer in water-air and soils compartments and on the other hand to highlight their contamination. Data concerning the water are more numerous cause of its status of ultimate receptacle of pollution and standards established by regulatory texts. The european Water Framework Directive (WFD) adopted in 2000 aims to achieve good chemical and ecological status of water bodies by 2015 with an obligation of results. The good chemical status depends on respect for the Environmental Quality Standards (EQS) established, for instance, for 24 pesticides. In 2012, 5% of river measurement points and 19%of groundwater measurement points do not respect these EQS. For many years, Languedoc Roussillon is the first wine-producing region of France and suffers from a significant pesticide pressure. In 2014, a report from the Regional Health Agency (RHA) has mentioned a relatively recent use of banned pesticides since the early 2000’s like simazin and terbutylazin. Moreover, RHA stated that most of recognized cases of non-compliance could be linked to the presence of agricultural activity in the catchment basin.[...] The establishment of POCIS devices on the three study sites showed the predominance ofpesticides used in viticulture and showed all the interest of the tool on a qualitative point ofview. The comparison of the tool with the automated sampling shows disparities between real concentration and concentration estimated with the POCIS. However, it remains to improvethe tool on a quantitative way to obtain a reliable and robust sampler for this type of exposure medium.

<p>Ispitani su hemijski sastav i biolo&scaron;ka aktivnost &scaron;est samoniklih vrsta iz tribusa Scandiceae<br />(familija Apiaceae): Anthriscus sylvestris, Anthriscus cerefolium, Chaerophyllum bulbosum,<br />Chaerophyllum hirsutum, Chaerophyllum temulentum i Scandix pecten-veneris. LC-MS-MS<br />analizom ekstrakata identifikovano je vi&scaron;e desetina sekundarnih biomolekula iz klasa flavonoida,<br />fenilpropenskih kiselina, lignana i kumarina. GC-MS analiza pružila je uvid u sastav volatilnih<br />komponenti i njihov hemosistematski značaj. Potvrđeno je da sve ispitivane vrste imaju umereno<br />antioksidantno, antiinflamatorno i antiproliferativno dejstvo.</p> / <p> Chemical composition and biological activity of six wild-growing species from<br /> Scandiceae tribe (Apiaceae family) &ndash; Anthriscus sylvestris, Anthriscus cerefolium, Chaerophyllum<br /> bulbosum, Chaerophyllum hirsutum, Chaerophyllum temulentum and Scandix pecten-veneris &ndash; was<br /> examined. By LC-MS-MS analysis, a large number of secondary biomolecules was identified in<br /> extracts, including flavonoids, phenylpropenic acids, lignans and coumarins. GC-MS analysis<br /> provided insight into volatile components composition and chemosystematic significance. All<br /> investigated species exhibited moderate antioxidant, anti-inflammatory and antiproliferative<br /> activity.</p>

No description available.

Plusieurs nouveaux complexes pinceurs de cobalt et de nickel ont été préparés avec le ligand pinceur de type POCOP : 2,6-(i-Pr2PO)2C6H4. Dans le cas du cobalt, une nouvelle voie de synthèse a été développée. Contrairement au cas du nickel, il s’agit ici de cobalt au degré d’oxydation +III. Les composés obtenus sont paramagnétiques. En outre, le dérivé bromé est instable à la lumière et se décompose en perdant un brome pour former le complexe pinceur de Co(II). La réactivité de ces complexes a été étudiée. Pour ce qui est du nickel, la catalyse de l’hydroamination a été élargie aux dérivés de l’acrylonitrile et aux amines aromatiques. En outre, la réaction d’hydroaryloxylation a été étudiée dans les mêmes conditions. Enfin, avec le 4-cyanostyrène et le cinnamonitrile, la formation d’amidines a été observée. Un complexe pinceur portant cette amidine a été isolé. Enfin, le cation réagit avec des anions fortement coordonnants tels le cyanure ou l’isocyanate. En outre, l’anion triflate peut être déplacé par l’eau, l’acrylonitrile et ses dérivés. Enfin, une réactivité particulière a été observée avec la morpholine, l’acétone et un mélange 1:1 aniline/triéthylamine. / A large variety of new POCOP pincer type complexes of cobalt and nickel have been prepared. All those complexes are based on the following POCOP pincer type ligand: 2,6-(i-Pr2PO)2C6H4 In the case of cobalt, a new synthetic pathway has been developped. Unlike nickel, complexes containing cobalt in the +III oxidation state are obtained, the mechanism of their formation remains unknown. These complexes are paramagnetic. The dibromo derivative is light-sensitive, decomposing by losing a bromine to form the Co(II) pincer complex. The reactivity of those complexes has been studied. Concerning nickel, the catalyzed hydroamination has been extended to the derivates of acrylonitrile, crotonitrile and methacrylonitrile and to aromatic amines. Moreover, hydroaryloxylation reaction has been studied under the same conditions. Finally, amidines formation was obtained with 4-cyanostyrene and with cinnamonitrile. A pincer complex bearing this amidine moiety has been isolated. The cationic complex reacts with strong coordinating anions like cyanide and isocyanate. Moreover, the triflate anion is displaced by water, acrylonitrile and acrylonitrile derivates. Finally, a particular reactivity has been observed with morpholine, acetone and a 1:1 mixture of aniline and triethylamine.

Die Geruchswahrnehmung von Insekten ist an die spezifischen Anforderungen der Ökosysteme angepasst, in denen sie leben. Von Insekten wahrgenommene Volatile können Informationen über den Ort eines geeigneten Ovipositionsplatzes oder den physiologischen Zustand einer Wirtspflanze geben. Da der Geruchssinn der Insekten sich seit Millionen von Jahren an die Wahrnehmung bestimmter Volatile angepasst hat, können die wahrgenommenen Volatile als Markerstoffe angesehen werden, die zuverlässig einen Ökosystemzustand angeben können. Die Identifikation dieser Markerzustände und die Evaluation ihrer Nützlichkeit für spurenanalytische Anwendungen ist das Ziel dieser Arbeit. Es wurden drei Themen ausgewählt um die Verwendungsmöglichkeit des Insektengeruchssinns für Sensoranwendungen zu überprüfen: Fleischfrische, Todeszeitbestimmung (post mortem Intervall, PMI) und frühzeitige Feuererkennung. Spurenanalytik (GC-MS), Elektrophysiologie (EAG, GC-MS/EAD), Verhaltensversuche und Feldtests wurden angewandt, um die chemoökologische Interaktion der Schmeißfliege Calliphora vicina und der „Feuerkäfer“ Melanophila cuspidata, Merimna atrata and Acanthocnemus nigricans mit ihrer natürlichen Umgebung zu untersuchen. Die Resultate aus diesen Methoden erlaubten die Selektion von Volatilen, die drei Kriteria erfüllen: hohe Quantität, zuverlässige Emission und die ausschliessliche Emission von der untersuchten und keiner anderen Quelle. Diese drei Auswahlkriterien wurden aufgestellt um zu gewährleisten, dass die ausgewählten Markervolatile nicht nur zuverlässig mit dem physiologischen Status der Substrate (Alter von verderbendem Fleisch, PMI, Temperatur von erhitzten Spänen) korrelieren, sondern auch den Ansprüchen technischen Sensorsysteme genügen. Im Falle des alternden Fleisches unter warmen und trockenen Bedingungen ist Nonanal ein Zeiger für die korrekte Reifung des Fleisches zu Schinken. Dimethyl Trisulfid, Phenol und Indol zeigen das Verderben des Fleisches unter warmen und feuchten Bedingungen an. Bei niedrigen Temperaturen sind zunehmende 2,3 Butandiol Emission und abnehmende Nonanal Emission ein Zeiger für zunehmendes Verderben des Fleisches, sowohl unter trockenen als auch feuchten Bedingungen. Allerdings wurde 2,3 Butandiol nicht von C. vicina wahrgenommen, da die Fliege während der Vegetationszeit aktiv ist und unter diesen Bedingungen Dimethyl Trisulfid, Phenol und Indol emittiert werden. Nonanal, Hexanal, Dimethyl Disulfid, Dimethyl Trisulfid, Butan-1-ol und Phenol wurden als nützliche Volatile zur Eingrenzung der Leichenliegezeit ausgewählt. Die genannten Aldehyde sind typisch für die frühen Stadien der Verwesung, gefolgt von Butan-1-ol und den Schwefelsulfiden. Phenol wird hauptsächlich in den späteren Verwesungsstadien emittiert. Allerdings werden Phenol und 1-Butanol nicht von der Fliege wahrgenommen, da diese ein Generalist ist und nicht zwischen dem geblähten und aktivem Stadium der Verwesung unterscheiden muss. Daher wird zusätzlich die Geruchswahrnehmung des Speckkäfers Dermestes maculans betrachtet. Die Untersuchung anderer necrophager Insekten können weitere Einblicke in die Zeitabhängigkeit der Volatilemissionen während der Vertebratenverwesung geben. Die im Rahmen dieser Arbeit gewonnenen Ergebnisse erlauben eine Korrelation zwischen Emissionen und Leichenliegezeit und können eine Grundlage für eine volatilenbasierte post mortem Zeitbestimmung für Polizeikräfte sein. Terpene, aliphatische Aldehyde, Furfural und Methoxyphenole werden von erhitztem Holz emittiert. Komponenten aus all diesen Stoffklassen werden von M. cuspidata und M. atrata wahrgenommen, da diese Käfer den Erhitzungszustand von Baumstämmen nach einem Feuer erkennen können, um einen geeigneten Ovipositionsplatz zu finden. A. nigricans nimmt vor allem Methoxyphenole wahr, wohingegen M. atrata und M. acuminata Furfural zur Orientierung verwenden. Diese Unterschiede komplementieren das bekannte Verhalten dieser Käfer in ihrer natürlichen Umgebung, da A. nigricans auf verkohlten Stämmen, die große Mengen von Methoxyphenolen emittieren, seine Eier ablegt, und M. atrata und M. cuspidata auf Stämmen ihre Eier ablegen, die vom Feuer zwar äußerlich verkohlt, aber innerlich nur erhitzt wurden und daher Furfural emittieren. Halbleitergassensoren, die Furfural mit einer ausreichenden Selektivität vermessen können, können Holzbrände schon während ansteigender Temperatur und damit vor der Entzündung detektieren. Derartige Sensoren können sowohl als neuartige Frühwarnsysteme für die holzverarbeitende Industrie als auch für Waldbrandwarnsysteme oder den Haushalt dienen.

This paper deals with the chemical identification of artefacts correlated with the process of ancient Egyptian mummification dating to the Graeco-Roman period. The samples were harvested from two artefacts belonging to the Museum of Mediterranean and Near Eastern Antiquities in Stockholm. The original description of the said samples defined them, as natron filled linen bags and bee product (honey?). To identify the true nature of the samples, advanced methods such as Fourier transform infrared spectrometry (FTIR), gas chromatography/mass spectrometry and powder X-ray Diffractometry were used. The results were correlated with previous made analyses regarding embalming materials to discover similarities. Furthermore, the research revealed that the previous sample identifications were false, while providing hypotheses based on the new results.

[pt] A matéria orgânica (MO) sedimentar de origem natural na Ria de Aveiro e no estuário Mondego foi caracterizada usando a composição elementar (C e N) e lipídios biomarcadores (esteróis, n-álcoois e triterpenoides). A contribuição por esgotos foi avaliada através de coprostanol e outros esteróis fecais. Amostras de sedimento superficial foram coletadas em 22 estações ao longo das regiões. Os lipídios biomarcadores foram extraídos, purificação com sílica-gel e analisados por cromatografia em fase gasosa acoplada a espectrometria de massas. O carbono orgânico total (9,94 e 43,00 mg g(-1)) teve uma correlação com o nitrogênio total (r(2) = 0,86). A razão C/N molar (14,34 mais ou menos 1,75) foi um valor típico de MO continental. Existe uma contribuição maior de MO terrestre nas amostras, como mostra as evidencias: a predominância de n-álcoois de cadeia longa (maior ou igual à C22), maior abundancia no somatório de sitosterol, estigmasterol e campesterol sobre outros fitoesterois, como o colesterol e o brassicasterol; e a alta concentração de triterpenoides de plantas superiores, como Beta-amirina e a Alfa amirina. A concentração de coprostanol (0,05 a 16,6 microgramas g(-1)) indicou a presença de esgotos em sete estações localizadas no largo do Laranjo (S4, S5, S6, S7, S10), porto de Aveiro (S14) e no canal de Ílhavo (S16). Os aportes mais significativos foram no largo do Laranjo (S8 e S9) e no porto do Mondego (S19). / [en] The sedimentary organic matter (OM) of natural origin in the Ria de Aveiro and the estuary of Mondego River was characterized using elemental composition (C and N) and lipid biomarkers (sterols, alcohols and triterpenoids). In addition, the contribution by sewage was evaluated by coprostanol and other fecal sterols. Surface sediment samples were collected at 22 stations along the two regions. The lipid biomarkers was extracted, separated with silica-gel and analyzed by gas chromatography coupled to mass spectrometry. Concentrations of total organic carbon (9.94 and 43.00 mg g(-1)) was highly correlated with total nitrogen (r(2) = 0.86). The C/N molar ratio: 14,34 plus-minus 1,75 are typical values of OM of continental origin. There is a major contribution of terrestrially OM to the sediments, as suggested by proxies, including: predominance of long-chain (greater-than or equal to C22) alcohols, higher abundance of sitosterol, estigmasterol and campesterol over other phytosterols, like cholesterol and brassicasterol, and elevated concentrations of triterpenoids from higher plants, as Beta-amyrin and Alpha-amyrin. The concentrations of coprostanol (0.05 to 16.6 micrograms g(-1)) indicated the presence of sewage in seven stations located in the Largo do Laranjo (S4, S5, S6, S7, S10), Port of Aveiro (S14) and in Ílhavo Channel (S16). The more significant contribution of sewage was identified in the Largo do Laranjo (S8 and S9) and the Port of Mondego (S19).