Les chondrites carbonées peuvent contenir jusqu'à 4% en masse de carbone, principalement présent sous la forme d'une fraction organique insoluble (MOI) enrichie en deutérium par rapport aux échantillons organiques terrestres. Cet enrichissement a été interprété comme la signature de processus interstellaires. La MOI est constituée d'unités aromatiques assez petites (de 2 à 3 cycles contigus) reliées entre elles par des chaînes aliphatiques courtes et ramifiées. La MOI d'Orgueil et de Murchison a été étudiée par des dégradations thermique et chimique, ainsi que par spectroscopie. Il apparaît à travers les données récoltées que les chaînes aliphatiques contiennent moins de 7 carbones et qu'elles sont très ramifiées. Par ailleurs, elles peuvent contenir des fonctions éther et ester. Ces chaînes peuvent lier deux ou trois unités aromatiques entre elles. Les chaînes aliphatiques non liantes (avec une extrémité libre) sont plus courtes: moins de 3 carbones. Les données acquises nous ont aussi permis de montrer que l'azote était contenu dans des hétérocycles. Cette observation, ainsi qu'une comparaison de données isotopiques, implique qu'il n'y a pas de lien génétique entre la MOI et les acides aminés présents dans la fraction soluble des météorites. Ceci n'exclut pas que d'autres classes de composés solubles puissent dériver de la MOI par altération hydrothermale sur le corps parent, ce qui indiquerait une origine complexe pour la fraction soluble. Le rapport isotopique D/H des briques élémentaires de la MOI d'Orgueil, obtenues par pyrolyse et dégradation chimique, a été interprété en considérant la macromolécule avant sa dégradation. Les résultats montrent que la MOI est un produit solaire et qu'elle s'est enrichie en D à la périphérie de la nébuleuse protosolaire sous des conditions proches du milieu interstellaire. Cette conclusion est majeure pour la MOI, qui a pu être la plus grosse partie de la matière organique abiotique sur la Terre primitive.

Made available in DSpace on 2014-06-11T19:31:35Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-05-16Bitstream added on 2014-06-13T20:42:02Z : No. of bitstreams: 1 figueira_r_dr_botfca.pdf: 569416 bytes, checksum: 1d15111b017c0b979c7ca67f95acf6b1 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O objetivo deste trabalho foi desenvolver o método de análise isotópica para a quantificação de fonte C3 em suco, néctar e refrigerante de maçã. Essas bebidas foram produzidas em laboratório, conforme a legislação brasileira. Também foram produzidos sucos adulterados (quantidade de açúcar de cana acima do permitido), néctares e refrigerantes adulterados (quantidade insuficiente de suco). Nessas bebidas, foram feitas análises de ºBrix, pH, acidez titulável, ratio, análise energética e análise isotópica. Para as análises isotópicas foi mensurado o enriquecimento isotópico relativo das bebidas de maçã bem como de suas frações (polpa lavada com água, polpa lavada com acetona e açúcar purificado extraído das bebidas de maçã). Com estes resultados foi estimada a quantidade de fonte C3 pela equação da diluição isotópica. Para determinar a legalidade das bebidas comerciais de maçã foi necessário a criação do limite de legalidade para separar as bebidas que estão de acordo com a legislação brasileira. Os valores da quantificação de fonte C3 acima do limite de legalidade foram considerados legais. Caso estes valores estejam abaixo deste limite, estes produtos foram considerados adulterados conforme as normas brasileiras. A metodologia desenvolvida para sucos, néctares e refrigerantes de maçã comerciais provou ser eficiente para separar os produtos que estão de acordo com a legislação. Esta metodologia também pode ser aplicada para verificar a legalidade em outras bebidas de frutas comerciais. / The goal of this work was to develop an isotopic analysis method to the C3 source quantification in juice, nectar and apple soft drink. In laboratory, juice, nectar and apple soft drink were produced according to Brazilian legislation. Also adulterated juices (cane sugar quantity up admitted), nectar and soft drink adulterated (insufficient juice quantity) were produced. In these beverages, analysis of ºBrix, pH, titratable acidity, ratio, energetic and isotopic analysis were made. For the isotopic analysis, the isotopic enrichment of apple beverages and fractions of this beverages (pulpy washed with water, pulpy washed with acetone and sugar purified extracted of apple beverages) were measured. With these results, the C3 quantification was estimated by the equation of isotopic dilution. For determine the legality of apple commercial beverages, the creation of legality limit for separate the lawful beverages was necessary. The values of C3 quantification above the legality limit were considerate lawful. If below of the legality limit were considerates unlawful according to the Brazilian rules. The methodology developed for commercial juices, nectars and apple soft drinks was efficient to separate the lawful beverages. This methodology can be applied for verify the legality in others commercial fruit beverages.

Made available in DSpace on 2014-06-11T19:31:35Z (GMT). No. of bitstreams: 0 Previous issue date: 2006-02-03Bitstream added on 2014-06-13T20:02:23Z : No. of bitstreams: 1 sleiman_m_dr_botfca.pdf: 830460 bytes, checksum: a045f031359bcdcbafd59a7f88312024 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Universidade Estadual Paulista (UNESP) / O objetivo deste trabalho foi desenvolver uma metodologia para quantificar a proporcao de malte e adjunto utilizada na elaboracao de cervejas do tipo Pilsen. Alem disso, verificou-se a possivel ocorrencia de fraude nas cervejas comerciais fabricadas no Brasil e foi avaliada a correlacao entre o percentual de malte com o preco de varejo da bebida. Para isso, foi testada a metodologia de isotopos estaveis atraves dos elementos quimicos carbono (13C) e nitrogenio (15N). Materias-primas cervejeiras (malte, grits de milho, quirera de arroz, xarope de maltose (HMCS) e acucar de cana), oriundas de diferentes regioes geograficas, foram usadas para a producao de mostos puros e misturas destes, a fim de produzir fermentados padroes de referencia para a construcao de gretas de calibracao-h, a partir das quais se propos um modelo de comportamento para a populacao de cervejas, atraves de analise de regressao linear invertida. Tambem foi calculado um intervalo de confianca ao nivel de 90% para a quantificacao do percentual mais provavel (PMP) de malte presente nas cervejas. Posteriormente, foram feitas analises isotopicas e fisico-quimicas de cervejas comerciais de dezessete estados brasileiros produtores da bebida. A partir dos resultados obtidos, concluiu-se que a cevada e o malte assemelham-se entre si para os dois isotopos analisados, nao sendo possivel sua diferenciacao. As analises de Â13C sao mais indicadas para 2 se calcular o PMP de malte para cervejas elaboradas com malte e adjunto proveniente de planta de ciclo fotossintetico C4, enquanto que as analises de Â15N sao recomendadas para o calculo do PMP de malte em amostras de cerveja elaboradas com malte e arroz (C3). Foram analisadas 161 amostras de cervejas, sendo que 91,3 % utilizaram malte e adjuntos derivados de planta de ciclo C4 em sua formulacao, 4,3 % apresentaram arroz... / The objective of this work was to develop a methodology to quantify the proportion of malt and the adjunct used in the Pilsen beer brewing, to verify the possible occurrence of fraud in beer brewed in Brazil and to evaluate the correlation between the percent of malt with the beer retail price. Therefore, the methodology of stable isotopes using the chemical elements carbon (13C) and nitrogen (15N) was tested. Raw material of beer (malt, corn grits, rice, high maltose corn syrup and sugar cane) coming from different geographical regions, were used for the production of pure worts and their mixtures. These mixtures turned fermented standards of reference to make calibration straight lines, from which a model was proposed by inverted linear regression analysis, that to conduct for all Pilsen beer. Also a range of trust was calculated at a level of 90 % to quantify the most likely percentage (MLP) of malt present in beer. After that, stable isotopic analyses and physical-chemical analyses were made of brewing beer from seventeen Brazilian States brewers of beer. The results showed that barley and malt are similar in the two analyzed isotopes, not being possible to separate them. The analysis of ä13C presented the MLP of malt in brewed beer with malt and the adjunct coming from the C4 plant, and the analysis of ä15N provided the MLP of malt in beer brewed with malt and rice (both C3 plant). One hundred sixty one samples of Brazilian beer were analyzed, from which 91,3 % used malt and adjuncts of the C4 plant in its formulation, 4,3 % showed rice, 4,3% were classify like pure malt beer. From the total, 28,6 % were in the doubt range as for the MLP of malt... (Complete abstract click electronic access below)

The Encounters and Transformations in Iron Age Europe project (ENTRANS) aims to expand our knowledge regarding the nature and impact of cultural encounters during the European Iron Age. The study of ceramic vessels was included in the project, in order to further understand cultural practices in the south-east Alpine region. Organic residue analysis is an important tool in archaeological research for determining the presence of food and other organic substances associated with ceramic vessels. It has the potential to significantly improve our understanding of Iron Age societies and the interactions between them. This research focuses on the analysis of visible and absorbed organic residues from 377 ceramic vessels, from Late Bronze Age and Early Iron Age sites in Slovenia and Croatia, by gas-chromatography mass spectrometry. Two methods of lipid extraction were compared in a pilot study compressing 30 potsherds from Kaptol (solvent vs. acid extraction). This study revealed that more information was obtained by acid extraction, thus it was selected as the main method of extraction for this project. Differences between settlement, funerary and ritual sites were observed, suggesting that the vessels placed in the graves were not previously used or carried foodstuff with low lipid content, such as liquids and dry foods/cereals. Some types of residues were only identified in funerary vessels, specifically potential castor oil in Kaptol, mixed with other fats and oils. Lipid biomarkers and lipid ratios revealed significant differences between contexts and different sites, suggesting that the differences in cultural practices can also be identified in the use of ceramic vessels. Some residues were also sampled for gas-chromatography compound-specific isotope ratio mass spectrometry and bulk isotope analysis (only visible residues), which identified potential dairy fats in two potsherds from Poštela. The results were also compared with the contextual information, mainly the faunal remains, and the data obtained from the osteology and diet study preformed with individuals from the same area and chronology as the ceramic vessels. / Encounters and Transformations in Iron Age Europe Project (ENTRANS); Humanities in the European Research Area (HERA); Institute Life Sciences Research (ILSR) University of Bradford.

Orientador: Waldemar Gastoni Venturini Filho / co- orientador : Carlos Ducatti / Banca: Léa Silvia Mara Sant'ana / Banca: Muris Sleiman / Banca: José Albertino Bendassolli / Resumo: O objetivo deste trabalho foi desenvolver o método de análise isotópica para a quantificação de fonte C3 em suco, néctar e refrigerante de maçã. Essas bebidas foram produzidas em laboratório, conforme a legislação brasileira. Também foram produzidos sucos adulterados (quantidade de açúcar de cana acima do permitido), néctares e refrigerantes adulterados (quantidade insuficiente de suco). Nessas bebidas, foram feitas análises de ºBrix, pH, acidez titulável, ratio, análise energética e análise isotópica. Para as análises isotópicas foi mensurado o enriquecimento isotópico relativo das bebidas de maçã bem como de suas frações (polpa lavada com água, polpa lavada com acetona e açúcar purificado extraído das bebidas de maçã). Com estes resultados foi estimada a quantidade de fonte C3 pela equação da diluição isotópica. Para determinar a legalidade das bebidas comerciais de maçã foi necessário a criação do limite de legalidade para separar as bebidas que estão de acordo com a legislação brasileira. Os valores da quantificação de fonte C3 acima do limite de legalidade foram considerados legais. Caso estes valores estejam abaixo deste limite, estes produtos foram considerados adulterados conforme as normas brasileiras. A metodologia desenvolvida para sucos, néctares e refrigerantes de maçã comerciais provou ser eficiente para separar os produtos que estão de acordo com a legislação. Esta metodologia também pode ser aplicada para verificar a legalidade em outras bebidas de frutas comerciais. / The goal of this work was to develop an isotopic analysis method to the C3 source quantification in juice, nectar and apple soft drink. In laboratory, juice, nectar and apple soft drink were produced according to Brazilian legislation. Also adulterated juices (cane sugar quantity up admitted), nectar and soft drink adulterated (insufficient juice quantity) were produced. In these beverages, analysis of ºBrix, pH, titratable acidity, ratio, energetic and isotopic analysis were made. For the isotopic analysis, the isotopic enrichment of apple beverages and fractions of this beverages (pulpy washed with water, pulpy washed with acetone and sugar purified extracted of apple beverages) were measured. With these results, the C3 quantification was estimated by the equation of isotopic dilution. For determine the legality of apple commercial beverages, the creation of legality limit for separate the lawful beverages was necessary. The values of C3 quantification above the legality limit were considerate lawful. If below of the legality limit were considerates unlawful according to the Brazilian rules. The methodology developed for commercial juices, nectars and apple soft drinks was efficient to separate the lawful beverages. This methodology can be applied for verify the legality in others commercial fruit beverages. / Doutor

Orientador: Waldemar Gastoni Venturini Filho / Banca: Carlos Ducatti / Banca: Marcelo Zacharias Moreira / Banca: Iraê Amaral Guerrini / Banca: João Batista de A. e Silva / Resumo: O objetivo deste trabalho foi desenvolver uma metodologia para quantificar a proporcao de malte e adjunto utilizada na elaboracao de cervejas do tipo Pilsen. Alem disso, verificou-se a possivel ocorrencia de fraude nas cervejas comerciais fabricadas no Brasil e foi avaliada a correlacao entre o percentual de malte com o preco de varejo da bebida. Para isso, foi testada a metodologia de isotopos estaveis atraves dos elementos quimicos carbono (13C) e nitrogenio (15N). Materias-primas cervejeiras (malte, grits de milho, quirera de arroz, xarope de maltose (HMCS) e acucar de cana), oriundas de diferentes regioes geograficas, foram usadas para a producao de mostos puros e misturas destes, a fim de produzir fermentados padroes de referencia para a construcao de gretas de calibracao-h, a partir das quais se propos um modelo de comportamento para a populacao de cervejas, atraves de analise de regressao linear invertida. Tambem foi calculado um intervalo de confianca ao nivel de 90% para a quantificacao do percentual mais provavel (PMP) de malte presente nas cervejas. Posteriormente, foram feitas analises isotopicas e fisico-quimicas de cervejas comerciais de dezessete estados brasileiros produtores da bebida. A partir dos resultados obtidos, concluiu-se que a cevada e o malte assemelham-se entre si para os dois isotopos analisados, nao sendo possivel sua diferenciacao. As analises de Â13C sao mais indicadas para 2 se calcular o PMP de malte para cervejas elaboradas com malte e adjunto proveniente de planta de ciclo fotossintetico C4, enquanto que as analises de Â15N sao recomendadas para o calculo do PMP de malte em amostras de cerveja elaboradas com malte e arroz (C3). Foram analisadas 161 amostras de cervejas, sendo que 91,3 % utilizaram malte e adjuntos derivados de planta de ciclo C4 em sua formulacao, 4,3 % apresentaram arroz... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The objective of this work was to develop a methodology to quantify the proportion of malt and the adjunct used in the Pilsen beer brewing, to verify the possible occurrence of fraud in beer brewed in Brazil and to evaluate the correlation between the percent of malt with the beer retail price. Therefore, the methodology of stable isotopes using the chemical elements carbon (13C) and nitrogen (15N) was tested. Raw material of beer (malt, corn grits, rice, high maltose corn syrup and sugar cane) coming from different geographical regions, were used for the production of pure worts and their mixtures. These mixtures turned fermented standards of reference to make calibration straight lines, from which a model was proposed by inverted linear regression analysis, that to conduct for all Pilsen beer. Also a range of trust was calculated at a level of 90 % to quantify the most likely percentage (MLP) of malt present in beer. After that, stable isotopic analyses and physical-chemical analyses were made of brewing beer from seventeen Brazilian States brewers of beer. The results showed that barley and malt are similar in the two analyzed isotopes, not being possible to separate them. The analysis of ä13C presented the MLP of malt in brewed beer with malt and the adjunct coming from the C4 plant, and the analysis of ä15N provided the MLP of malt in beer brewed with malt and rice (both C3 plant). One hundred sixty one samples of Brazilian beer were analyzed, from which 91,3 % used malt and adjuncts of the C4 plant in its formulation, 4,3 % showed rice, 4,3% were classify like pure malt beer. From the total, 28,6 % were in the doubt range as for the MLP of malt... (Complete abstract click electronic access below) / Doutor

No / RATIONALE: The carbon isotopic characterisation of ruminant lipids associated with ceramic vessels has been crucial for elucidating the origins and changing nature of pastoral economies. delta(13)C values of fatty acids extracted from potsherds are commonly compared with those from the dairy and carcass fats of modern domesticated animals to determine vessel use. However, the processing of wild ruminant products in pottery, such as deer, is rarely considered despite the presence of several different species on many prehistoric sites. To address this issue, the carbon isotope range of fatty acids from a number of red deer (Cervus elaphus) tissues, a species commonly encountered in the European archaeological record, was investigated. METHODS: Lipids were extracted from 10 modern red deer tissues obtained from the Slowinski National Park (Poland). Fatty acids were fractionated, methylated and analysed by gas chromatography/combustion/isotope ratio mass spectrometry (GCCIRMS). The delta(13)C values of n-octadecanoic acid and n-hexadecanoic acid, and the difference between these values (Delta(13)C), were compared with those from previously published ruminant fats. RESULTS: Nine of the ten deer carcass fats measured have Delta(13)C values of less than -3.3 per thousand, the threshold previously used for classifying dairy products. Despite considerable overlap, dairy fats from domesticated ruminants with Delta(13)C values less than -4.3 per thousand are still distinguishable. CONCLUSIONS: The finding has implications for evaluating pottery use and early pastoralism. The processing of deer tissues and our revised criteria should be considered, especially where there is other archaeological evidence for their consumption.

no / During the micro-excavation of the cauldrons, residues were identified which appeared different from the surrounding soil and metal corrosion products. Thirty-seven of these residues from nine cauldrons and two significant fragments of incomplete cauldrons were analysed by gas chromatography-mass spectrometry (GC-MS) along with two samples of soil from the micro-excavation for comparison. The aim of the analysis was to determine whether these residues contained any organic material related to the use of the cauldrons, specifically lipids (fats, waxes, resins etc.) from the preparation of food or drink. Two of the samples from the cauldrons were also sent for compound specific carbon stable isotope analysis by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) to give a more precise identification of the residues.

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