The late Palaeocene to late Eocene period of Earth's history is characterised by remarkable change. Temperate ice free poles at the beginning of this period gradually cooled until permanent ice formed on Antarctica around 33.5 million years before present (Ma) and sea ice formed in the Arctic. The intervening time was not stable and data, despite relatively low resolution, appear to show that the Eocene climate was dynamic. This period was the most recent time when atmospheric pCO2 concentrations were as high as predicted by models simulating the effects of anthropogenic fossil fuel burning on Earths' climate. The ability to understand the mechanisms of climate change in the Eocene will help to understand potential climate impacts in the future. This thesis examines 3 contrasting periods of climate change. Geochemical data indicate that a 3.5 million year period of high biogenic silica deposition during the Eocene was climatically relatively stable in the Arctic basin with only infrequent communication to the world's oceans outside. This period is correlated with high organic burial in the basin and global siliceous rich deposits which acted to gradually draw down pCO2. This period of `quiet' climate compares to two periods of warming where significant carbon isotope perturbations may indicate the forcing of the Earth's climate into an alternative quasi-stable state. The Palaeocene { Eocene Thermal Maximum (PETM) represents a significant input of exogenic carbon into the atmosphere over the course of several thousand years and significant warming of the Earth. Records of bulk carbonate isotopes from a section in NE Italy show several other Delta13C perturbations both before and after the PETM event, albeit a quarter to a half of the magnitude of the PETM, and having durations of only 40 { 60 thousand years (kyr). These events are thought to be the result of a re-arrangement of the internal carbon cycle of the Earth - atmosphere and may represent orbitally forced changes in deep water ocean ventilation similar to controls seen on modern day glacial { interglacial cycles. These rapid changes in the carbon cycle are shown to be inverse at the middle Eocene Climatic Optimum (MECO), where gradual warming over 400 kyr is ended abruptly by significant cooling. From the first marginal marine section of this event rapid organic carbon burial occurs over 50 { 100 kyr and is associated with previously unrecorded low oxygen bottom water conditions and high organic burial. We hypothesize that if this burial was extended over significant shelf areas then this could rapidly have returned the middle Eocene to the general cooling trend of the Eocene.

The Butia odorata has received special attention from the scientific community because of their nutritional and functional properties that have been revealed, in addition to its rightdown sensory characteristics. The aim of this study was to characterize different genotypes from Butia odorata fruit collected in Santa Maria - RS (SM) and Santa Rosa - RS (SR) regions during three consecutive harvests in relation to various physical and chemical properties. Many analyses were performed like: biometric, color and quality parameters, fatty acid composition in the Butia pulp. An HS-SPME method was developed for the isolation and subsequent quantification (GC-FID) and identification (GC/MS) of volatile compounds (VCs). The biometric parameters results showed pulp yields between 40.38 and 73.91%. The color of the pulp ranged between yellow and orange shades. TSS ranged between 12.39 and 15.50 °Brix, acidity between 0.69 and 2.26 g% citric acid and pH between 3.17 and 3.95. The fruit had humidity between 78.04 and 85.85 g%; ashes between 0.47 and 0.77 g%; protein between 0.57 and 0.93 g%, crude fiber between 0.84 and 4.02 g%; lipid between 0.12 and 2.27 g%. The fatty acids such as palmitic acid, linoleic and linolenic acids were found in abundance. It was possible to observe the partial discrimination between the two regions in the PCA using the physico-chemical variables. The samples from SR characterized by high scores for lipids and palmitic acid, while SM samples showed a higher humidity and TSS. The method employed use DVB/CAR/PDMS fiber for the VCs extraction of the centrifuged Butia pulp , added with 30% NaCl, and maintaining the system at a temperature of 35 °C for 45 minutes, under stirring. The volatile fraction was analyzed in GC and were identified 77 compounds among acids (5), alcohols (14), aldehydes (9), ketones (12), lactones (3), terpenes (2) and esters (34). The ethyl hexanoate compound was the major compound in almost samples. The PCA from VCs enabled to realize grouping of samples into two groups according to region of origin. The fruits from Santa Maria showed a high content of esters and the fruits from Santa Rosa had higher concentrations of alcohols and aldehydes. An exploratory analysis of the variables of physico-chemical composition and volatile of the samples was observed using PCA. In the graphs analysis also realized a partial separation of samples according to their region: the samples SM2-10 and RS1-11 distanced themselves from the other and it indicates greater particularity in their chemical compositions. Therefore the fruits (Butia odorata) showed great variability in biometric characteristics, physico-chemical and volatile profiles according to region of origin. It indicates a strong influence of soil and climatic factors. In this study, the nutritional characteristics and high yield pulp of some Butia fruits demonstrated the high potential for fresh consumption or for the manufacture of processed products / O butiá (Butia odorata) tem recebido especial atenção da comunidade científica, em virtude de suas propriedades nutritivas e funcionais que estão sendo reveladas, além das suas características sensoriais peculiares, ainda pouco exploradas. Desta forma, o objetivo do presente trabalho foi caracterizar diferentes genótipos de frutos de butiazeiros coletados nas regiões de Santa Maria RS (SM) e Santa Rosa RS (SR) em três safras consecutivas, quanto as diversas propriedades físicoquímicas. Foram realizadas análises biométricas, de cor, dos parâmetros de qualidade, composição centesimal e ácidos graxos da polpa do butiá, além do desenvolvimento de método de isolamento por SPME com posterior quantificação (GC-FID) e identificação (GC/MS) dos compostos voláteis (CVs). Os resultados dos parâmetros biométricos revelaram rendimentos de polpa, entre 40,38 e 73,91%. A cor da polpa oscilou em tons de amarelo e laranja. Os SST variaram entre 12,39 e 15,50 °Brix, a acidez entre 0,69 e 2,26 g% em ácido cítrico e o pH entre 3,17 e 3,95. As frutas apresentaram umidade entre 78,04 e 85,85 g%; cinzas entre 0,47 e 0,77 g%, proteína entre 0,57 e 0,93 g%, fibra bruta entre 0,84 e 4,02 g% e lipídios de 0,12 a 2,27 g%. Os ácidos graxos encontrados em maior abundância foram o ácido palmítico, linoléico e linolênico. Na Análise dos Componentes Principais (PCA) empregando as variáveis físico-químicas observou-se a discriminação parcial entre as duas regiões, sendo as amostras da região de SR caracterizadas por elevados escores para lipídios e ácido palmítico, enquanto que as da região de SM apresentaram, em geral, maior umidade e teor de SST. O método desenvolvido emprega o uso da fibra DVB/CAR/PDMS para a extração dos CVs da polpa de butiá centrifugada, adicionada de 30% de NaCl, e mantendo o sistema a uma temperatura de 35 ºC por 45 minutos, sob agitação. A fração volátil foi analisada em GC e nela identificados 77 compostos entre ácidos (5), alcoóis (14), aldeídos (9), cetonas (12), lactonas (3), terpenos (2) e, principalmente, ésteres (34). Entre estes se destacou o hexanoato de etila como composto majoritário. A PCA dos CVs possibilitou ver o agrupamento das amostras em dois grupos conforme a região de origem, onde, em geral, os butiás de Santa Maria apresentaram elevado teor de ésteres, enquanto os de Santa Rosa obtiveram maiores concentrações de alcoóis e aldeídos. Uma análise exploratória entre as variáveis de composição físico-química e volátil das amostras estudadas foram observadas através de uma PCA. Na visualização dos gráficos notou-se também uma parcial separação das amostras quanto à região de origem, sendo que as amostras SM2-10 e SR1-11 distanciaram-se das demais, indicando maior particularidade em suas composições químicas. Sendo assim, os butiás apresentaram grande variabilidade em suas características biométricas, físicoquímicas e nos perfis voláteis em função da região de origem e safra e, portanto, apresentou forte influência de fatores edafoclimáticos. Sobretudo, as características nutricionais e o alto rendimento de polpa de alguns frutos de butiás evidenciaram, neste estudo, o alto potencial para consumo in natura ou mesmo para a fabricação de produtos processados.

Submitted by Amanda Silva (amanda.osilva2@ufpe.br) on 2015-03-05T13:29:04Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO Rafael Thompson de Oliveira Lemos.pdf: 1078520 bytes, checksum: 8a4e2b9b01b627e15dc3df1bd4ca084c (MD5) / Made available in DSpace on 2015-03-05T13:29:04Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) DISSERTAÇÃO Rafael Thompson de Oliveira Lemos.pdf: 1078520 bytes, checksum: 8a4e2b9b01b627e15dc3df1bd4ca084c (MD5) Previous issue date: 2013 / CNPq / O Estuário de Suape está localizado no litoral sul de Pernambuco, Brasil, cerca de 40 km da capital Recife. Este estuário está presenciando um rápido desenvolvimento industrial e portuário nas últimas décadas, com a implantação do Complexo Industrial Portuário de Suape (CIPS). Várias empresas instaladas na região operam cargas com derivados de petróleo, representando uma potencial fonte de hidrocarbonetos para o estuário. Amostras de água e sedimento foram coletadas com o objetivo principal de avaliar a presença de hidrocarbonetos no Estuário de Suape, identificando suas fontes e concentrações, em duas estações do ano (chuvosa e seca). As concentrações de hidrocarbonetos de petróleo dissolvidos e/ou dispersos na água foram determinadas usando a técnica de UV-Fluorescência. Os resultados variaram entre 0,05 e 4,59 μg L-1 equivalentes em óleo Carmópolis e entre 0,01 e 1,39 μg L-1 equivalentes em criseno, sugerindo que a região ainda pode ser classificada como não poluída. Algumas concentrações relativamente altas (>1 μg L-1) estão possivelmente associadas a resíduos originados nas atividades portuárias e do estaleiro, bem como a eventuais descargas industriais e lançamentos de resíduos de óleo por embarcações de pesca ou lazer. As concentrações de hidrocarbonetos de petróleo na água foram significativamente menores durante o período chuvoso, provavelmente devido a maior diluição dos contaminantes causada pelo aumento da precipitação e do fluxo de água doce no Rio Massangana. As concentrações de hidrocarbonetos alifáticos (HAs) foram determinadas no sedimento através da técnica de cromatografia em fase gasosa acoplada a um detector de ionização em chama (GC-FID) e os hidrocarbonetos policíclicos aromáticos (HPAs) foram determinados através de cromatografia em fase gasosa acoplada a um detector de espectrometria de massas (GC-MS). Os HAs variaram entre <LD e 27,15 μg g-1, e as concentrações de n-alcanos (C12-C35) variaram entre <LD e 6,84 μg g-1. Os resultados indicaram que o material orgânico proveniente de plantas superiores foi a principal fonte de hidrocarbonetos alifáticos, porém sinais de óleo degradado também foram observados em alguns sedimentos. As concentrações de HPAs variaram entre 4,25 e 888,42 ng g-1, e são relativamente baixas quando comparadas a estuários cronicamente impactados. As maiores concentrações foram encontradas próximas do quebra-mar na saída sul do estuário e estão provavelmente relacionadas ao transporte dos contaminantes levados pelas correntes para esta área de menor hidrodinâmica, que favorece a maior deposição dos mesmos. Além disto, os processos de dragagem não ocorrem neste local possibilitando um maior acúmulo de contaminantes. Os resultados indicaram que os HPAs encontrados nos sedimentos são provenientes de duas fontes distintas: introdução direta do petróleo e de compostos gerados em processos pirolíticos, através da queima de combustíveis ou matéria orgânica. Concentrações relativamente elevadas foram observadas para alguns HPAs individuais, representando moderada probabilidade em causarem danos à biota local. Este estudo mostra que as atividades desenvolvidas no estuário de Suape associadas à presença de manguezais na região contribuem para a introdução de hidrocarbonetos, mesmo que em baixas concentrações. Entretanto, devido ao crescente desenvolvimento do CIPS, incluindo a refinaria Abreu e Lima que iniciará suas operações em breve, é essencial que um programa de monitoramento contínuo seja implantado.

The Abraham solvation parameter model is a good approach for analyzing and predicting biological activities and partitioning coefficients. The general solvation equation has been used to predict the solute property (SP) behavior of drug compounds between biological barriers. Gas chromatography (GC) retention time can be used to predict molecular descriptors, such as E, S, A, B & L for existing and newly developed drug compounds. In this research, six columns of different stationary phases were used to predict the Abraham molecular descriptors more accurately. The six stationary phases used were 5% phenylmethyl polysiloxane, 6% cyanopropylphenyl 94% dimethylpolysiloxane, 5% diphenyl 95% dimethylpolysiloxane, 100% dimethylpolysiloxane, polyethylene glycol and 35% diphenyl 65% dimethylpolysiloxane. Retention times (RT) of 75 compounds have been measured and logarithm of experimental average retention time Ln(RTexp) are calculated. The Abraham solvation model is then applied to predict the process coefficients of these compounds using the literature values of the molecular descriptors (Acree Compilation descriptors). Six correlation equations are built up as a training set for each of the six columns. The six equations are then used to predict the molecular descriptors of the illegal drugs as a test set. This work shows the ability to extract molecular information from a new compound by utilizing commonly used GC columns available with the desired stationary phases. One can simply run the new compound in GC using these columns to get the retention time. Plugging in the retention time into the developed equations for each of the column will predict the molecular descriptors for the test compound and will give some information about the properties of the compound.

This thesis was focused on study of biotechnological utilization of waste substrates to produce lipids by yeast of the genus Metschnikowia. Waste materials and their subsequent transformation into high value-added products such as microbial lipids are currently considered as an alternative source for biofuel production. Therefore, the experimental part was aimed at investigating the influence of a carbon source to the controlled overproduction of lipids by yeast Metschnikowia. Total of 12 yeast strains of the genus Metschnikowia were selected. Yeast strains M. pulcherrima , M. pulcherrima 147, M. pulcherrima 149, M. andauensis 129 a M. fructicola 15 were purchased from Culture Collection of Yeasts (CCY, Bratislava, Slovakia). The growth characteristics of this yeast strains were also studied. It may serve to better understanding of the physiology of the yeast strains and also to help in further analysis of the produced metabolites. The other strains M. chrysoperlae 1158, M. pulcherrima 1232, M. fructicola 1235, M. andauensis 1241, M. sinensis 1244, M. zizyphicola 1247 a M. shanxiensis 1250 were purchased from CBS (Centraalbureau voor Schimmelcultures, Utrecht, the Netherlands).Yeast strains were cultivated on crude animal fat, glycerol and cheese whey under conditions of different C/N ratios. Because of higher lipid yields, cultivation was carried out at 14°C for 14 days. The accumulated lipid content was determined by gas chromatography and Raman spectroscopy. The glycerol-containing medium was evaluated as the most suitable for microbial lipids production. The total amount of lipids present in cells of M. pulcherrima 1232 was 36,31%. At the same time, quantitative screening of lipase enzymatic activity in Metschnikowia yeast was performed using spectrophotometric method with p-NPP. Controlled production of lipolytic enzymes has been monitored by using two types of media: crude animal fat and crude animal fat with addition of emulsifier (Tween 80). The conclusion of the work was supplemented by analysis of the karyotype of yeasts of the genus Metschnikowia using the technique of pulsed gel electrophoresis.

This diploma thesis addresses the presence and determination of chloramphenicol residues in biological materials. The theoretical part presents the literature retrieval containing information about veterinary medicaments with the banned use in food producing animals and also the sum of the legislative requirements concerning the presence of these substances in foodproducts and raw food materials of animal origin. The comparison was carried out between the existing analytical methods used for the determination of chloramphenicol residues in different biological materials, which are altogether based on the solid phase extraction for the extract cleaning and the new procedures for sample preparations using columns where the sorbent performs on the molecularly imprinted polymers principle.

Volatile sulphur substances originating during technological processes in malt and beer production can be a cause of various off-flavors and aromas. Their precursors are sulphur-containing amino acids. Sulphur substances play an important role in brewing as even in very low concentrations they can negatively affect total character of beer. Therefore, it is necessary to monitor volatile sulphur substances and their precursors to eliminate undesirable processes. Because sulphur substances occur in beer and raw materials at trace levels, microanalytical methods are used for their detection. This diploma thesis describes the problems of sulphur substances and their determination using the SPME/GC method.

The aroma compounds suitable for food flavouring are mainly of plant origin. It is necessary to take into account the possible allergic effects of some of them. The theoretic part of this thesis is focused on aroma compounds and their biological effects. It also describes methods useful for their isolation and analysis with a nearer intent on the methods used in this thesis - solid phase microextraction and gas chromatography. The aim of the experimental part was to establish, optimise and validate the method for determination of allergic aroma compounds chosen and subsequently to enable its using in wide spectrum of food and other products.

This thesis deals with the determination of fatty acids of processed cheese analogues. The aim is to identify and quantify the fatty acids in selected samples of cheese analogues. The introduction is a brief overview of the composition and properties of cheese analogues, technology and application options. The following describes the appropriate method for the determination of fatty acids in cheese and cheese analogues. Of these methods the largest part is devoted to gas chromatography, which is most frequently used method for detection of volatile fatty acids. Individual cheese analogues used for the analysis, contained various types of added fats. Specifically, the milk fat, coconut oil, sunflower oil, palm oil and butter. Samples of these fats were extracted and then converted to methylesters by methanol esterification with catalysis by potassium hydroxide. The most important fatty acids were identified and quantified in samples of cheese analogues using gas chromatography and compared with fatty acids of fats used for the preparation of these analogues are used.

The aim of the diploma thesis was the aroma active compounds assessment and sensory profile determination of various types of sea buckthorn (Hippopha rhamnoides L.). The theoretical part provides the detailed description of this plant, comprising the occurence, taxonomy, chemical composition and use. Experimental part summarizes the data obtained: identification and quantification of aroma compounds using the SPME – GC –FID and GC-MS method and evaluation of complete sensory profile. Various cultivars of sea buckthorn harvested in 2009-2012 were analysed. In total 23 various types of sea buckthorn were measured, 23 alcohols, 10 aldehydes, 11 esters, 14 ketones and 5 acids were found.