This paper deals with three mediaeval churches in the town Visby, Gotland. These churches were located in different areas in Visby. Allegedly the areas where St Hans and Ste Gertrud were located were inhabited by wealthier people, and the more peripheral area where St Mikael was located was where the poor lived. Therefore, the people that were buried at St Mikael should be of lower social status than the people buried at St Hans and Ste Gertrud. Based on the fact that an individuals diet was dependant on his or hers social status, dietary studies on skeletal remains from the three different churches have been conducted to find out dietary patterns among the individuals buried at each church respectively. The studies have included stable isotope ratio analyses, δ13C and δ15N, in human bone collagen. The results support the hypothesis that there were differences between individuals buried at different churches as stated above.

Made available in DSpace on 2014-10-09T12:51:55Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:15Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:51:55Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:15Z (GMT). No. of bitstreams: 0 / Este trabalho descreve a preparação, caracterização e certificação de um conjunto de materiais de referência isotópicos de urânio na faixa de 0,5 a 20,0 % de 235U em massa. Os principais conceitos da metrologia em medições químicas foram aplicados para que as propriedades certificadas nos materiais pudessem ser rastreáveis diretamente ao Sistema Internacional de Unidades (SI). Em conseqüência desta abordagem, estes materiais poderão ser utilizados na calibração de instrumentos de medição, avaliação da incerteza de medição, validação de métodos analíticos, avaliação da performance de analistas, rotinas de controle de qualidade e em programas de intercomparação de resultados de medição. As mais avançadas técnicas e métodos de espectrometria de massas, a saber, espectrometria de massas com fonte de gás (GSMS), espectrometria de massas por termoionizacão (TIMS) e espectrometria de massas com fonte de plasma induzido (ICPMS) foram investigadas para identificar quais são os componentes dominantes na incerteza e quantificar a sua contribuição no valor final da incerteza de medição da razão isotópica. Os resultados obtidos foram comparados entre si, para verificar quais técnicas e métodos estão associados aos menores valores de incerteza de medição. A razão isotópica n(235U)/n(238U) nos materiais produzidos foi certificada com incertezas de medição expandidas na faixa de 0,02 a 0,10 % e as razões n(234U)/n(238U) e n(236U)/n(238U), com incertezas na faixa de 0,03 a 2,20 %. Estes valores atendem plenamente aos requisitos da caracterização isotópica do combustível nuclear, bem como aos requisitos das análises de amostras ambientais para fins de salvaguardas nucleares. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Em ambientes poluídos como a região metropolitana de São Paulo é imprescindível o conhecimento da natureza da poluição para que sejam estabelecidos procedimentos de minimização ou de controle das emissões. O estudo da poluição atmosférica já vem sendo realizado há muitos anos, sendo os componentes inorgânicos estudados a partir da determinação em amostras coletadas em filtros, soluções, entre outros meios. Neste trabalho é apresentado um método de determinação da razão isotópica de enxofre utilizando a técnica da Espectrometria de Massas com Plasma de Argônio como fonte de íons. O uso de um espectrômetro de massas de dupla focalização com fonte de íons por plasma de argônio, HR-ICPMS, o qual atinge resoluções (m/&#916;m) de até 8000, permitiu a resolução dos pfcoS dos isótopos 32S e 34S das interferência isobáricas mais comuns e/ou intensas, assim as medições foram realizadas utilizando-se diretamente as m/z dos isótopos do enxofre: A discriminação de massa foi avaliada analisando-se o material de referência NIST 8555 Sulfeto de Prata. A discriminação de massa em elementos leves como é o caso do enxofre é mais acentuada do que para os mais pesados. Assim, uma solução do material de referência era analisada a cada seqüência de 5 ou 6 soluções das amostras. A razão isotópica do enxofre foi determinada em amostras de ar atmosférico coletadas em Sâo Paulo, Ilha Rei George; na Península Antártica e diretamente do escapamento de um carro movido a gasolina e a diesel, utilizando-se um amostrador de grandes volumes e um conjunto de filtros composto de: um filtro de fibra de vidro para a coleta da fração grossa seguido de dois filtros de celulose impregnados com uma mistura de KOH e trietanolamina para a coleta do SO2 e sua oxidação a SO42-. Dois procedimentos de extração dos compostos de enxofre foram utilizados: uma somente com água e outra mais enérgica com ácido nítrico em forno de microondas. Os resultados obtidos indícaram que os dois procedimentos de extração resultam em soluções com composição isotópica diferentes. Além disso, a razão isotópica entre as soluções provenientes dos filtros de fibra de vidro e de celulose são também diferentes. Provavelmente, devido ao fracionamento existente em função da forma química do enxofre presente preferencialmente numa fração ou noutra. A análise quantitativa dos metais revelou uma presença de Fe em concentrações altas (5000-20000 ng/m3), enquanto que os demais (Mn, Cu, Cr, Ni, V, Sr, Cd, Co, Nd, Gd, Ir, Rh, Zr, Re e Ag) estavam presentes em concentrações mais baixas (< 300 ng/m3). Pelas características da amostragem, o Fe foi associado à ressuspensão do solo. O Nd, Gd, Ir, Rh, Re e Ag puderam ser tanto associados à ressuspensão do solo quanto à emissões por automóveis. O Mn, Cu, Cr, Ni, V e Sr foram associados à emissões devido à queima de combustíveis fósseis. / Polluted areas like the Great São Paulo nave a compltex pollution composition. The knowledge of this composition is essential in order to minimize or controt tne dífferent sources. Several atmospheric pollution studies have been done analyzing the inorganic fraction in samples collected in filters, solutions and other media. In this study, the sulfur isotopic ratio determination by using the mass spectrometry with an argon plasma as a source of ions is presented. A double focusing sector field mass spectrometer with an argon plasma, HR-ICPMS, was used. Since 8000 resolution (m/&#916;m} can be achieved, the 32S and 34S sulfur isotopes can be directly measured with no interferences from the common isobaric interferences (oxygen compounds). Tne isotopic ratio was determined in materials collected by using a high volume sampler. These samples were collected in São Paulo, in the King George Island; Antarctic and directly from the gases exhaust of agasoline and diesel vehicles. Two different filters were used : an external glass fiber filter was used to collect the gross fraction followed by two KOH-Triethanolamine impregnated cellulose filter to collect S)2. Two extraction procedures were used. The first one is an energetic extraction with nitric acid and micro-wave heating and the second one only with water being the soluble sulfur compounds extracted from the filters after had left 24 hours in a beaker with water. Mass discrimination was evaluated by analyzing the NlST 8555 Silver Sulphide Reference Material. As the mass discrimination is more prominent in light elements, the reference material solution was analyzed within a sequence of 5 or 6 samples. The results indicated dífferent isotopic ratio between the solutions obtained with these two extraction procedures. Different isotopic ratios were also observed in the sulfur isotopic composition in the gross and the fine fraction. This is probably due to different sulfur species present preferentially in a given fraction. The quantitative analyses of metals revealed a high Fe concentration (5000-20000 ng/m3) and lower concentrations (<300 ng/m3) to the others (Mn, Cu, Cr, Ní, V, Sr, Co, Co, Ncf, Go, Ir, Rh, Zr, Re and Ag). lron was associated to the soil dust. Neodymium, Gd, Ir, Rh, Re and Ag were associated to the soil dust and to the vehicles emissions. Manganese, Cu, Cr, Ni, V and Sr were associated to the vehicles emissions.

A dual phase gas diffusion-FIA system containing a tubular PTFE-membrane was studied as a mean of producing gas samples for routine 15N/14N isotopic ratio mass spectrometry. The method is based on Rittenberg's reaction; the ammonium sample is injected into a liquid alkaline stream containing hypobromite and the N2 gas produced in the reaction diffuses across a PTFE-membrane into a helium carrier stream which carries it to the detector. Initially here, the use of a tubular microporous PTFE-membrane as a device for the preconcentration of samples in aqueous solutions was investigated. The performance of such a membrane was studied under a variety of operating conditions. A qualitative model of the membrane mechanism was developed based on the diffusion transport of vapour away from the contained liquid surface through the connected pore space. The dispersion undergone by the sample in the GD-FIA system containing this preconcentration unit was also studied and this FIA system was applied as a practical device for the determination and speciation of aluminium in a river water sample. The procedure for generating nitrogen gas involved optimisation of the system parameters including the oxidation reaction step and the production on-line of the chemicals used. The nitrogen gas was generated easily and rapidly, allowing a sample throughput capability of the order of 20 h-1. The system was applied to the determination of total nitrogen content in agricultural sample prepared by the Kjeldahl digestion. The method offered precision and accuracy comparable to those of the standard distillationtitration procedure. Isotope ratios were determined with good precision and means for obtaining accuracy comparable with established techniques were developed. It was also shown that the DPGD-FIA system can be readily adapted to enable different forms of nitrogen e. g. N02-, N03- and NH4+ to be determined.

No / We examined multiple natural abundance isotope ratios of human hair to assess biological variability within and between geographic locations and, further, to determine how well these isotope values predict location of origin. Sampling locations feature differing seasonality and mobile populations as a robust test of the method. Serially-sampled hair from Cambridge, MA, USA, shows lower δ2 H and δ18 O variability over a one-year time course than model-predicted precipitation isotope ratios, but exhibits considerable differences between individuals. Along a ∼13° northsouth transect in the eastern USA (Brookline, MA, 42.3 ° N, College Park, MD, 39.0 ° N, and Gainesville, FL, 29.7 ° N) δ18 O in human hair shows relatively greater differences and tracks changes in drinking water isotope ratios more sensitively than δ2 H. Determining the domicile of humans using isotope ratios of hair can be confounded by differing variability in hair δ18 O and δ2 H between locations, differential incorporation of H and O into this protein and, in some cases, by tap water δ18 O and δ2 H that differ significantly from predicted precipitation values. With these caveats, randomly chosen people in Florida are separated from those in the two more northerly sites on the basis of the natural abundance isotopes of carbon, nitrogen, hydrogen, and oxygen. / This work was partially supported by the National Geospatial Agency under grant [HM1582-08-0024]. / Originally presented at the IAEA International Symposium on Isotope Hydrology: Revisiting Foundations and Exploring Frontiers, 11–15 May 2015, Vienna, Austria

Brominated organic compounds (BOCs) of both natural and anthropogenic origin are abundant in the environment. Most compounds are either clearly natural or clearly anthropogenic but some are of either mixed or uncertain origin. This thesis aims to identify some naturally produced BOCs and to develop a method for analysis of the bromine isotopic composition in BOCs found in the environment. Polybrominated dibenzo-p-dioxins (PBDDs) in the Baltic Sea are believed to be of natural origin although their source is unknown. Since marine sponges are major producers of brominated natural products in tropical waters, BOCs were quantified in a sponge (Ephydatia fluviatilis) from the Baltic Sea (Paper I). The results showed that the sponge does not seem to be a major producer of PBDDs in the Baltic Sea. In this study, mixed brominated/chlorinated dibenzo-p-dioxins were however discovered for the first time in a background environment without an apparent anthropogenic source. The use of nuclear magnetic resonance spectroscopy (NMR) is unusual in analytical environmental chemistry due to its sample requirements. Preparative capillary gas chromatography was used to isolate a sufficient amount of an unidentified BOC from northern bottlenose whale (Hyperoodon ampullatus) blubber (Paper II) to enable NMR analysis for identification of the compound. The bromine isotopic composition of BOCs may give information on the origin and environmental fate of these compounds. The first steps in this process are the development of a method to determine the bromine isotope ratio in environmentally relevant BOCs (Paper III) and measuring the bromine isotope ratio of several standard substances to establish an anthropogenic endpoint (Paper IV). / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

No description available.

Neste trabalho foram estudados vinhos provenientes de microvinificações das variedades Merlot e Cabernet Sauvignon das sub-regiões de Pinto Bandeira, Vale dos Vinhedos, Nova Pádua e Monte Belo do Sul, nas safras de 2005 e 2006. Foram determinadas as razões isotópicas 13C/12C do etanol e 18O/16O da água e do etanol, buscando possível diferenciação entre as variedades e safras de produção, e provável relação entre o local de origem e suas características geográficas (altitude e latitude) e climatológicas (temperatura, precipitação pluviométrica e umidade). Utilizou-se um espectrômetro de massas de razão isotópica (IRMS) acoplado a um analisador elementar, para análise de 13C/12C do etanol e 18O/16O da água e a um cromatógrafo gasoso, para análise de 18O/16O do etanol. Em relação aos valores de δ13C, observou-se que a diferenciação entre as sub-regiões amostrais são menos seletivas e não seguem mesma ordem estatística encontrada para as análises δ18O, porém a análise de δ13C do etanol pode servir para diferenciar sub-regiões que não são diferenciadas estatisticamente pelas análises de δ18O. O comportamento dos valores de δ18O da água e do etanol obedecem mesma ordem estatística de diferenciação. Independente da variedade de uva utilizada neste trabalho, foi possível diferenciar as sub-regiões através da análise isotópica de δ18O, nas duas safras de produção, com exceção do Vale dos Vinhedos e Monte Belo do Sul, safra 2005, que não apresentaram diferenças estatísticas. As latitudes das diferentes sub-regiões apresentaram diferença estatística e demonstraram influência principalmente nos valores de δ18O da água. As análises de δ18O da água e do etanol do vinho mostraram-se mais seletivas e eficientes na discriminação das sub-regiões de cultivo do que as análises de δ13C do etanol. Foi observada uma forte correlação entre os valores de δ18O da água e do etanol. A altitude e a latitude influenciam principalmente os valores de δ18O da água e do etanol. As influências climáticas são mais marcantes na distinção entre safras de produção do que sub-regiões de cultivo. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-05-14T18:11:59Z No. of bitstreams: 1 Dissertacao Laurien Adami.pdf: 946622 bytes, checksum: 1405d2dd9ccbcd048e59ac45e36fd0f7 (MD5) / Made available in DSpace on 2014-05-14T18:11:59Z (GMT). No. of bitstreams: 1 Dissertacao Laurien Adami.pdf: 946622 bytes, checksum: 1405d2dd9ccbcd048e59ac45e36fd0f7 (MD5) / In this work, wines provided by micro-winemakings of the variety Merlot and Cabernet Sauvignon of the sub-regions of Pinto Bandeira, Vale dos Vinhedos, Nova Pádua and Monte Belo do Sul in the 2005 and 2006 harvest have been studied. It has been established the isotopic ratios 13C/12C of the ethanol and 18O/16O of the water and ethanol, seeking for a possible differentiation among the varieties and production harvests, and a possible relation between the place of origin and its geographic features (altitude and latitude) and climatological conditions (temperature, precipitation and humidity). It has been used a isotope ratio mass spectrometer (IRMS) coupled to an elementar analyzer for the analysis of the 13C/12C of the ethanol and 18O/16O of the water and to a gas chromatograph for the analysis of 18O/16O of the ethanol. In relation to the values of δ13C, it is observed that the differentiation among the sampling sub-regions are less selective and do not follow the same statistical order found for the analysis of δ18O, however, the analysis of δ13C of the ethanol may be used to differentiate sub-regions that are not differentiated statistically by the analysis of δ18O. The value behaviors of δ18O of the water and the ethanol follow the same statistical order of differentiation. Regardless of the grape variety used in this work, it has been possible to differentiate the sub-regions through the isotopic analysis of the δ18O, in both production harvests, except for the Vale dos Vinhedos and Monte Belo do Sul, 2005 harvest, which did not present statistical differences. The latitudes of the different sub-regions presented statistical differences and demonstrated an influence mainly in the values of δ18O of the water. The analysis of δ18O of the water and the ethanol of the wine conveyed to be more selective and efficient in the discrimination of the cultivation sub-regions than the analysis of δ13C of the ethanol. It has been observed a strong correlation between the values of δ18O of the water and the ethanol. The altitude and latitude influence mainly the values of δ18O of the water and the ethanol. The climate influences are more noteworthy in distinguishing the production harvests than the cultivation sub-regions.

La nutrition azotée des bactéries et des plantes est actuellement un sujet de grande importance, notamment pour comprendre comment améliorer les voies métaboliques aboutissant à l’assimilation de l’azote et à plus grande échelle, optimiser des apports d’engrais et augmenter le rendement des cultures. Dans ce contexte, la réaction d’amidation catalysée par la glutamine synthétase (GS), qui fixe l’ammonium (NH₄)⁺ en glutamine, est cruciale car elle est à la fois le point d’entrée de l’azote dans les végétaux, et une étape-clef du recyclage de l’azote (en particulier, NH₄⁺ photorespiratoire). Dans cette étude, nous nous sommes intéressés à la cinétique enzymatique et au mécanisme chimique de la GS. Des systèmes analytiques (HPLC, RMN , GC-MS) ont  été optimisés pour permettre la mesure de l’activité enzymatique in vitro et pour réaliser des analyses par spectrométrie de masse à ratio isotopique. Avec ces techniques, nous avons pu regarder précisément les effets isotopiques ¹²C/¹³C, ¹⁴N/¹⁵N et H₂O/D₂O (solvant) lors de la catalyse, en utilisant la GS d’E. coli et d’Arabidopsis thaliana (GS1,2). Nos résultats montrent qu’il n’y a pas d’effet isotopique ¹²C/¹³C, mais qu’il y a un fractionnement ¹⁴N/¹⁵N de »16‰. En outre, il y a un effet inverse du solvant (réaction 1.5 à 2 fois plus rapide dans D₂O).  Cela suggère que la création de la liaison C----N (amidation) est partiellement limitante (engagement catalytique de »14% seulement) et que le réseau de ponts hydrogènes dans le site actif est crucial pour déterminer la vitesse de la réaction. L’apparition d’effets ¹⁴N/¹⁵N inverses dans certaines circonstances et les effets drastiques causés par une substitution du cofacteur métallique (Mg²⁺) suggèrent en outre que l’étape d’amidation peut être réversible et que la coordination par un métal joue un rôle très important pour stabiliser les intermédiaires de la réaction, en interaction avec le solvant. Ainsi, dans son solvant naturel qu’est H₂O, la GS réalise une réaction ‘chimiquement difficile’ (barrière énergétique élevée de l’amidation) rendue possible par le clivage de l’ATP et son caractère exergonique. / Nitrogen nutrition in bacteria and plants is currently an important topic, in particular to identify key points for metabolic improvements in N assimilation and more generally, to optimize fertilization and crop yield. In such a context, the amidation reaction catalyzed by glutamine synthetase (GS), which fixes ammonium (NH₄)⁺ into glutamine, is of crucial importance since it both represents the N entry in plants and the main step of N recycling (such as photorespiratory (NH₄)⁺. Here, we examined GS kinetics and chemical mechanism. Analytical methods (HPLC, NMR, GC-MS) have been set up so as to measure in vitro activities and isotopic abundance by isotope ratio mass spectrometry. These gave access to isotope effects (¹²C/¹³C, ¹⁴N/¹⁵N et H₂O/D₂O – solvent) during catalysis, with the GS from either E. coli or A. thaliana (GS1,2). Our results show that there no ¹²C/¹³C isotope effect but there is significant ¹⁴N/¹⁵N isotope fractionation of ca. 16‰. In addition, there is an inverse solvent isotope effect (reaction 1.5 to 2 times faster in D₂O). This suggests that forming the C----N bond (amidation) is partially rate-limiting (catalytic commitment of ca. 14% only) and the H-bond network in the active site is of substantial importance for the reaction rate. The occurrence of inverse ¹⁴N/¹⁵N isotope effects under certain circumstances as well as the drastic impact of changing the metal cofactor (Mg²⁺)) indicate that the amidation step can be reversible and that the coordination by the metal plays a key role in stabilizing reaction intermediates, by interfacing the solvent. In other words, in its natural solvent H₂O, the GS catalyses an intrinsically ‘difficult’ reaction (high energy barrier of amidation) made possible by both ATP cleavage and its exergonic nature.