Thesis (Ph. D.)--Oregon Graduate Center, 1979.

Reconstructing diet in Andean populations is complicated by ecological complexity and by large-scale population movements and trade networks during the period of imperial rule. It is therefore more difficult to reconstruct dietary patterns within these contexts. Previous multi-isotopic analysis of the skeletal population from the Inca site of Machu Picchu indicates marked variation in dietary composition both early and late in life. However, these data are limited in their specificity due to overlap in isotopic signals from different resource types. I compare existing isotopic data to enamel macro- and microwear data to more accurately profile diet composition in a Machu Picchu skeletal population subset. Results suggest there is little to no dietary variation between sexes and age groups. Results also reveal the role that maize played in the diet of this non-elite population, which may prove useful in more accurately estimating consumed food resources in this and other Andean populations.

Rivers are a significant source of particulate and dissolved organic carbon (POC, DOC) into inland waters and coastal systems and provide a fundamental linkage between the terrestrial, oceanic, and atmospheric carbon reservoirs. Recent studies have examined the relationship between the quantity and form (POC vs. DOC) of carbon delivered to the aquatic system; however, little is known about the age of POC and DOC exported and how the radiocarbon age may vary with latitude, topographic gradient, vegetation, and land use. I provide the first global synthesis of published radiocarbon values of POC and DOC (∆14C). Inclusion of DOC and POC parameters (µM, δ13C, ∆14C) reveal significant driving forces of DOC (µM), latitude, and elevation (m) as capable of explaining 25% of the variability in DO14C in rivers and POC (µM) and latitude accounting for 15% of the variability in PO14C. When δ13C of DOC and POC and latitude were incorporated with ∆14C of DOC observations, 61% of the variability in DOC age was explained revealing the necessity to include dissolved and particulate fractions of organic carbon to yield the most robust predictive models. This study found a global trend of increasing age of DOC and increasing δ13C of DOC and POC with increasing latitude. My study suggests future research should incorporate both particulate and dissolved OC parameters along with elevation, vegetation, land cover, and climate zones to increase understanding of what drives the age of carbon exported in riverine systems.

Neste trabalho foi estabelecido um procedimento para determinação da razão isotópica 238U/235U em amostras de UF6, utilizando-se um espectrômetro de massas quadrupolar com ionização por impacto eletrônico e detecção de íons por copo de Faraday ou multiplicador de elétrons. Para tanto, o espectrômetro foi otimizado, determinando-se os parâmetros para a fonte de íons que proporcionassem a maior intensidade de corrente iônica, mantendo o pico de forma arredondada, para a massa correspondente ao isótopo mais abundante; a resolução que reduzisse os efeitos não lineares e o número de ciclos analíticos que reduzisse a incerteza nos resultados. O processo de medição foi caracterizado quanto: aos efeitos de discriminação de massa, linearidade e efeito memória. A discriminação de massas mostrou ser linearmente dependente da pressão da amostra no tanque de expansão nas faixas de 0,15 a 0,30 mbar e de 0,30 a 0,40 mbar. O espectrômetro mostrou-se linear na medição de razões isotópicas entre 0,005 e 0,045. Os fatores de memória para a fonte de íons e para o sistema de introdução são, respectivamente, 1,000 ± 0,001 e 1,003 ± 0,003; o primeiro pode ser desprezado e o segundo eliminado por procedimentos de lavagem do sistema de introdução. O trabalho apresenta, em sua parte final, um roteiro para as análises de amostras de UF6 e a determinação das incertezas nos resultados. / In the present work a procedure for determination of the isotopic ratio 238U/235U in UF6 samples was established using a quadrupole mass spectrometer with ionization by electron impact and ion detection by Faraday cup or electron multiplier. For this, the following items were optimized in the spectrometer: the parameters in the íon source that provided the most intense peak, with good shape, for the corresponding mass of the most abundant isotope; the resolution that reduced the non linear effects and the number of analytic cycles that reduced the uncertainty in the results. The measurement process was characterized with respect to the effects of mass discrimination, linearity and memory effect. The mass discrimination showed to be linearly dependent of the sample pressure in the batch volume, for the pressure ranges from 0.15 to 0.30 mbar and from 0.30 to 0.40 mbar. The spectrometer was shown linear in the measurement of isotopic ratios between 0.005 and 0.045. The memory factor for the íon source and for the introduction system were, respectively, 1.000 ± 0.001 and 1.003 ± 0.003; the first one can be ignored, the second one can be eliminated by washing the batch volume with the new sample. A methodology for routine analysis of UF6 samples and the determination of the uncertainties were set up in details as well.

Neste trabalho foi estabelecido um procedimento para determinação da razão isotópica 238U/235U em amostras de UF6, utilizando-se um espectrômetro de massas quadrupolar com ionização por impacto eletrônico e detecção de íons por copo de Faraday ou multiplicador de elétrons. Para tanto, o espectrômetro foi otimizado, determinando-se os parâmetros para a fonte de íons que proporcionassem a maior intensidade de corrente iônica, mantendo o pico de forma arredondada, para a massa correspondente ao isótopo mais abundante; a resolução que reduzisse os efeitos não lineares e o número de ciclos analíticos que reduzisse a incerteza nos resultados. O processo de medição foi caracterizado quanto: aos efeitos de discriminação de massa, linearidade e efeito memória. A discriminação de massas mostrou ser linearmente dependente da pressão da amostra no tanque de expansão nas faixas de 0,15 a 0,30 mbar e de 0,30 a 0,40 mbar. O espectrômetro mostrou-se linear na medição de razões isotópicas entre 0,005 e 0,045. Os fatores de memória para a fonte de íons e para o sistema de introdução são, respectivamente, 1,000 ± 0,001 e 1,003 ± 0,003; o primeiro pode ser desprezado e o segundo eliminado por procedimentos de lavagem do sistema de introdução. O trabalho apresenta, em sua parte final, um roteiro para as análises de amostras de UF6 e a determinação das incertezas nos resultados. / In the present work a procedure for determination of the isotopic ratio 238U/235U in UF6 samples was established using a quadrupole mass spectrometer with ionization by electron impact and ion detection by Faraday cup or electron multiplier. For this, the following items were optimized in the spectrometer: the parameters in the íon source that provided the most intense peak, with good shape, for the corresponding mass of the most abundant isotope; the resolution that reduced the non linear effects and the number of analytic cycles that reduced the uncertainty in the results. The measurement process was characterized with respect to the effects of mass discrimination, linearity and memory effect. The mass discrimination showed to be linearly dependent of the sample pressure in the batch volume, for the pressure ranges from 0.15 to 0.30 mbar and from 0.30 to 0.40 mbar. The spectrometer was shown linear in the measurement of isotopic ratios between 0.005 and 0.045. The memory factor for the íon source and for the introduction system were, respectively, 1.000 ± 0.001 and 1.003 ± 0.003; the first one can be ignored, the second one can be eliminated by washing the batch volume with the new sample. A methodology for routine analysis of UF6 samples and the determination of the uncertainties were set up in details as well.

Yes / A rare, intact Viking boat burial in western Scotland contained a rich assemblage of grave goods, providing clues to the identity and origins of both the interred individual and the people who gathered to create the site. The burial evokes the mundane and the exotic, past and present, as well as local, national and international identities. Isotopic analysis of the teeth hints at a possible Scandinavian origin for the deceased, while Scottish, Irish and Scandinavian connections are attested by the grave goods. Weapons indicate a warrior of high status; other objects imply connections to daily life, cooking and work, farming and food production. The burial site is itself rich in symbolic associations, being close to a Neolithic burial cairn, the stones of which may have been incorporated into the grave. / The accepted post-review manuscript here was submitted under the title: "The Viking boat burial on Ardnamurchan".

Les hydrocarbures aromatiques polycycliques (HAP), sont des molécules toxiques, voire cancérigènes principalement issues de la combustion incomplète de matière carbonée. De nombreux outils ont été développés afin d’identifier leurs origines et leur devenir. Cependant, ces derniers ne permettent pas toujours de parvenir à une identification précise des sources d’émissions. Une méthode prenant en compte les variations des rapports isotopiques δ 13C et δ 2H dans 16 composés a été développée et comparée à celle des ratios moléculaires. Le développement du protocole a consisté en la préparation puis la validation d’une méthode d’extraction sélective par type de matrice (eau/sédiment) et d’une méthode de purification permettant d’obtenir pour chaque molécule une résolution adaptée à leur analyse isotopique. Cette méthode a été appliquée sur divers produits de combustion franciliens ainsi que sur des échantillons de dépôts atmosphériques, d’eau et de sédiments de rivière. La mesure du δ13C et du δ2H a permis de confirmer la présence de sources locales et de caractériser les variations saisonnières de ratios. L’originalité de ce travail de recherche réside dans l’utilisation du δ2H spécifique à chaque molécule et non sur un mélange de composés. Les résultats permettent d’envisager de nouvelles perspectives sur l’utilisation des mesures isotopiques. Cette thèse représente un premier élément de réponse sur la problématique de l’emploi d’outils de traçage de molécules dans des environnements complexes. / Polyaromatic hydrocarbons (PAHs) are a group of toxic and carcinogenic organic compounds formed by petrogenic and incomplete pyrolytic processes. Although emission reductions were observed over the past 20 years, PAH contamination is still an environmental concern as these compounds are the main contaminants in the Seine watershed. Many tools were developed to identify their origins and fate. However, these methods do not always allow accurate identification of emission sources. A method integrating the variations of the isotopic ratios of δ13C and δ2H among 16 compounds was developed and compared to those of the molecular diagnostic ratio techniques. The development of the protocol consisted of the preparation and the validation of a selective extraction method by matrix type (water / sediment) and a purification step to obtain for each molecule, a resolution adapted to its isotopic analysis. That method applied to various combustion products in the Ile-de-France region, such as samples of atmospheric deposition, water and river sediments. The measurement of δ13C and δ2H signatures confirmed the presence of local sources and helped to characterize the seasonal variations of the ratios. The originality of this research work is the use of δ2H on individual PAH instead of bulk compounds. The results allow considering new perspectives for the use of isotopic measurements.

Made available in DSpace on 2017-07-10T17:30:42Z (GMT). No. of bitstreams: 1 Paula_Ewald.pdf: 4676802 bytes, checksum: c77cee71420720dcbe5dd9d247b3cb6a (MD5) Previous issue date: 2015-06-02 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In the Quaternary period, the south of Brazil has suffered from paleoclimate instabilities which have generated changes in the landscape. Pedological, sedimentological and paleoenvironmental reconstructions studies have been developed by the group Gênese e Evolução de Superfícies Geomórficas e Formações Superficiais - UNIOESTE-FB to investigate the paleoclimate influence on the landscape setting of the Southwest region in Paraná and Northwest region in Santa Catarina States. Aiming to contribute with these studies, this research has sought to investigate the evolution of the vegetation at Ecological Station Mata Preta in Abelardo Luz (Santa Catarina State) and to verify the hypothesis of occurrence of vegetation changes over the Holocene in the studied area. Specifically, the goal was to determine the phytolith signature of the current vegetation and to assess its variability in the superficial soil horizons under the Mixed Ombrophylous Forest (FOM - Araucaria Forest) and to know the historical trajectory of the changes in the vegetation of the area of study during the Holocene Era. Routine physical and chemical analyses have been used to characterize a soil profile and phytolith and isotopic analyses (δ13C of the soil organic matter - SOM and datation14Cof humin fraction) in a soil profile (Profile 1) and more three Control Points (PC1, PC2 and PC3). The physical and chemical analyses of the soil allowed the classification of the studied soil as a Humic Dystrophic Inceptisol. The values of δ13C of the SOMpointed to a vegetation change between the Middle Holecene and the Late and the phytolith assembly of the soil allowed the refining of this interpretation. Thus, it is possible to infer that his soil registers a period during which the vegetation was formed by a prevailing community of C4plants (more open than the current one), in the Middle/Early Holocene (6.235-6.215 years Cal. AP), evolving to a mixed vegetation, more forested and similar to the current one, composed, predominantly, of C3plants, in the Late Holocene (from 840 to 835 years cal. A.P.) which evolved to the current FOM. Based on the litterphytolith assemblage and on the superficial layers of the Inceptisol and the PC´s, it has been defined the phytolith signature of the FOM, which is formed by 14 morphotypes of phytoliths which represent the families of Poaceae (subfamilies Panicoid; Pooid; Chloridoid and Bambusoid), Eudicotiledoneae, Arecaceae and Cyperaceae. / No período Quaternário, o Sul do Brasil passou por instabilidades paleoclimáticas que geraram mudanças nas paisagens. Estudos pedológicos, sedimentológicos e de reconstrução paleoambiental têm sido desenvolvidos pelo grupo Gênese e Evolução de Superfícies Geomórficas e Formações Superficiais (UNIOESTE-FB) para investigar a influência paleoclimática na configuração da paisagem do Sudoeste do Paraná e Noroeste de Santa Catarina. Visando contribuir com estes estudos, a presente pesquisa buscou investigar a evolução da vegetação na Estação Ecológica Mata Preta em Abelardo Luz (SC) e verificar a hipótese de ocorrência de trocas de vegetação ao longo do Holoceno na a área estudada. Especificamente, objetivou-se determinar a assinatura fitolítica da vegetação atual e avaliar a sua variabilidade nos horizontes superficiais do solo sob a Floresta Ombrófila Mista FOM (Mata de Araucária) e conhecer a trajetória histórica das mudanças da vegetação da área de estudo durante a Época Holocênica. Foram empregadas análises físicas e químicas de rotina para caracterização de um perfil de solo e análises fitolíticase isotópicas (δ13C da matéria orgânica do solo e datação 14C da fração humina) em um perfil de solo (Perfil 1) e em três Pontos de Controle (PC1, PC2 e PC3). As análises físicas e químicas do solo permitiram classificar o solo estudado como um CAMBISSOLO HÚMICO. Os valores de δ13C da matéria orgânica do solo (MOS) apontaram para uma troca de vegetação entre o Holoceno Médio e o Superior e a assembleia fitolítica do solo permitiu o refinamento dessa interpretação. Assim é possível inferir que este solo registra uma fase em que a vegetação era formada por uma comunidade predominantemente de plantas C4 (vegetação mais aberta que a atual), no Holoceno Médio/Inferior (6.235-6.215 anos Cal. AP), evoluindo para uma vegetação mista, mais florestada e semelhante à atual, composta predominantemente por plantas C3 no Holoceno Superior (de 840 e 835 anos cal. A.P) que evoluiu para a atual FOM. Com base na assembleia fitolítica da serrapilheira e das camadas superficiais do Perfil de CAMBISSOLO e dos PC, definiu-se a assinatura fitolítica da FOM, que é formada por 14 morfotipos de fitólitos representativos das famílias Poaceae (subfamílias Panicoid; Pooid; Chloridoid e Bambusoid), Eudicotiledoneae, Arecaceae e Cyperaceae.

Στο πεδίο κρατήρων του Κόλπου του Ελαιώνα, παρατηρήθηκε διαφυγή γλυκού νερού (Christodoulou et al., 2002). Προκειμένου να διαπιστωθεί αν ο παράκτιος υδροφόρος εκφορτίζεται στη θάλασσα, έγινε δειγματοληψία νερού σε πηγές και γεωτρήσεις στη χέρσο και πραγματοποιήθηκαν υδροχημικές και ισοτοπικές αναλύσεις. / Groundwater seepage was observed in the pockmark field in Eleonas Bay (Christodoulou et al., 2002). In order to find out if the coastal aquifer seeps through the seafloor, water samples were taken from springs and boreholes and hydrochemical and isotopic analyses took place.

En complément des analyses de concentration et de spéciation, les analyses des isotopes stables du mercure par MC-ICP-MS sont à l’heure actuelle un outil majeur pour tracer les sources et les transformations de cet élément dans l’environnement. Cette thèse propose le développement de techniques de pré-concentrations couplées au MC-ICP-MS afin de réaliser des analyses isotopiques de mercure au niveau du ng.L-1 (Ultra-trace). La stratégie de pré-concentration en ligne va générer des signaux transitoires courts dont la gestion en MC-ICP-MS représente un réel défi. Afin d’y répondre, une méthode de traitement de données adaptée à ce type de signaux ainsi qu’une méthode de correction du phénomène de dérive isotopique ont été développées. Dans le but de déterminer des compositions isotopiques en mercure total à de faibles concentrations, le couplage d’une génération de vapeur froide, d’une double amalgamation sur or (CVG-DGA) et d’un MC-ICP-MS a été développé. Cette nouvelle technique donne des précisions externes de l’ordre de 0.20 à 0.30‰ (2SD) pour des concentrations en mercure de 5 ng.L-1 en solution. Cette thèse présente également une nouvelle méthode d’analyse isotopique par espèce chimique (CSIA) réalisée à l’aide du couplage d’une chromatographie en phase gazeuse équipée d’un injecteur PTV (GC-PTV) et d’un MC-ICP-MS. Celle-ci permet l’analyse isotopique de plusieurs espèces chimiques avec des précisions externes de l’ordre de 0.30 à 0.40‰ (2SD) pour des concentrations en mercure de 150 ng.L-1 dans des échantillons biologiques.Les développements analytiques de cette thèse ont permis de mesurer directement et de façon automatisée des compositions isotopiques de mercure à des niveaux d’ultra-trace (jusqu’à 5ng.L-1) tout en conservant des précisions compatibles avec les principales questions environnementales posées. Ceci va permettre d’analyser des compartiments environnementaux contenant de faibles quantités de mercure (eaux naturelles, planctons,…) et ouvre ainsi de nouvelles perspectives pour une meilleure compréhension du cycle bio-géochimique du mercure. / In addition to the quantitative and speciation analysis, the analysis of mercury stable isotopes by MC-ICP-MS are now a tool of choice to track sources and pathways of this element in the environment. This PhD thesis presents the development of hyphenation between pre-concentration techniques and MC-ICP-MS to measure isotopic composition of mercury at ng.L-1 levels (Ultra-trace). The on-line pre-concentration strategy will create short transient signals which represent a real challenge for MC-ICP-MS. In order to solve it, a data treatment strategy for this particular signals and a correction method for the isotopic drift were developed.The hyphenation between a cold vapor generation, a dual gold amalgamation (CVG-DGA) and a MC-ICP-MS was developed to determine total mercury isotopic composition. This new technique gives external precisions ranging from 0.20 to 0.30‰ (2SD) for Hg concentration in solution of 5 ng.L-1. This PhD thesis also reports a new method to perform mercury compound specific isotopic analysis (CSIA) using a gas chromatography fitted with a PTV injector (GC-PTV) coupled to the MC-ICP-MS. This allows the isotopic analysis of several species with external precisions ranging from 0.30 to 0.40‰ (2SD) for mercury concentration down to 150 ng.L-1 in biological samples.The analytical developments proposed in this PhD thesis allows to automatically and directly measure mercury isotopic compositions at ultra-trace levels (down to 5 ng.L-1) while keeping precision compatible with main environmental questions. This will allow to analyze environmental compartment containing very low amount of mercury (natural waters, planktons,…) and then open new perspectives for a better understanding of the bio-geochimical cycle of mercury.