O objetivo primário deste estudo é aprimorar o conhecimento acerca das fontes do manto e dos mecanismos envolvidos na gênese dos basaltos da Província Magmática do Paraná, que constitui uma das maiores manifestações de basaltos continentais do mundo. Para tanto, foram determinadas as concentrações de terras raras (La, Ce, Nd, Sm, Eu, Tb, Yb e Lu), outros elementos traço (Cs, Rb, Ba, U, Th, Ta, Hf, Co e Sc) e elementos altamente siderófilos (Os, Ir, Ru, Pt, Pd e Re), juntamente com razões isotópicas dos sistemas Rb-Sr, Sm-Nd, U-Th-Pb e Re-Os em basaltos com alto-Ti (Paranapanema e Pitanga) que ocorrem no norte da PMP. Além disso, foram determinadas as concentrações de elementos altamente siderófilos e as razões isotópicas de 187Os/188Os amostras representativas de basaltos com baixo-Ti (Esmeralda) do sul da PMP. Os dados geoquímicos e as razões isotópicas de Sr, Nd e Pb obtidos são consistentes com dados da literatura, porém, refinam as variações (extremos) isotópicas dos magmas-tipo Paranapanema e Pitanga. Esses dados, juntamente com as concentrações de elementos altamente siderófilos e das razões isotópicas de Os, inéditas na literatura, sugerem que as fontes dos basaltos (astenosfera ou manto litosférico subcontinental) sofreram metassomatismo significativo, com a intrusão de veios piroxeníticos, relacionado a antigas subducções e/ou processos de delaminação. / The primary goal of this study is to improve the understanding about the mantle sources and the mechanisms involved in the basalt genesis from Paraná Magmatic Province (PMP), which is one of the largest known continental flood basalts of the world. Therefore, the concentrations of rare earths (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu), other trace elements (Cs, Rb, Ba, U, Th, Ta, Hf, Co and Sc) and highly siderophile elements (Os, Ir, Ru, Pt, Pd and Re) were determined, along with isotope ratios regarding Rb-Sr, Sm-Nd, U-Th-Pb e Re-Os systematics in high-Ti basalts (Paranapanema and Pitanga) from northern PMP. In addition, the highly siderophile element concentrations, as well as 187Os/188Os isotope ratios, were measured in selected samples of low-Ti basalts (Esmeralda) from southern PMP. The geochemical and Sr-Nd-Pb isotope results of the present study are consistent with literature data, but refine the isotope variations (extreme) for the Paranapanema and Pitanga magma-types. These data, along with the concentrations of highly siderophile elements and Os isotope ratios suggest that the basalt mantle sources (asthenosphere or subcontinental lithospheric mantle) were affected by significant metasomatism (piroxenitic vein hybridization), related with old subduction and/or delamination processes.

Sections in and around Badlands National Park, Custer County, South Dakota contain a wealth of faunal and floral data within the White River Group. The Chadronian and Orellan North American Land Mammal Ages define the Eocene-Oligocene boundary here. Faunal and floral changes associated with the Chadronian-Orellan interval have long been attributed to the global Greenhouse-Icehouse climatic transition. Stable isotopes were obtained from paleosol carbonates across the Chadronian-Orellan boundary at three locations in Badlands National Park. Results show wide fluctuations of oxygen isotopes in the uppermost Chadronian and lower Orellan, while carbon isotopes remain relatively stable. The records provide an opportunity to compare the continental response to global change with a near-shore marine system response (Gulf Coastal Plain, USA); and to the world at large. Results indicate a decoupling of the terrestrial response to the Oi-1 glacial event from the marine response. Local conditions appear to play an important role in controlling the record of stable isotopes in paleosol carbonates in the region. / Geologic history of the Eocene-Oligocene -- Climate records -- Causes of climate change -- Climate change across the Eocene-Oligocene -- Current findings -- Discussion. / Department of Geology

O objetivo primário deste estudo é aprimorar o conhecimento acerca das fontes do manto e dos mecanismos envolvidos na gênese dos basaltos da Província Magmática do Paraná, que constitui uma das maiores manifestações de basaltos continentais do mundo. Para tanto, foram determinadas as concentrações de terras raras (La, Ce, Nd, Sm, Eu, Tb, Yb e Lu), outros elementos traço (Cs, Rb, Ba, U, Th, Ta, Hf, Co e Sc) e elementos altamente siderófilos (Os, Ir, Ru, Pt, Pd e Re), juntamente com razões isotópicas dos sistemas Rb-Sr, Sm-Nd, U-Th-Pb e Re-Os em basaltos com alto-Ti (Paranapanema e Pitanga) que ocorrem no norte da PMP. Além disso, foram determinadas as concentrações de elementos altamente siderófilos e as razões isotópicas de 187Os/188Os amostras representativas de basaltos com baixo-Ti (Esmeralda) do sul da PMP. Os dados geoquímicos e as razões isotópicas de Sr, Nd e Pb obtidos são consistentes com dados da literatura, porém, refinam as variações (extremos) isotópicas dos magmas-tipo Paranapanema e Pitanga. Esses dados, juntamente com as concentrações de elementos altamente siderófilos e das razões isotópicas de Os, inéditas na literatura, sugerem que as fontes dos basaltos (astenosfera ou manto litosférico subcontinental) sofreram metassomatismo significativo, com a intrusão de veios piroxeníticos, relacionado a antigas subducções e/ou processos de delaminação. / The primary goal of this study is to improve the understanding about the mantle sources and the mechanisms involved in the basalt genesis from Paraná Magmatic Province (PMP), which is one of the largest known continental flood basalts of the world. Therefore, the concentrations of rare earths (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu), other trace elements (Cs, Rb, Ba, U, Th, Ta, Hf, Co and Sc) and highly siderophile elements (Os, Ir, Ru, Pt, Pd and Re) were determined, along with isotope ratios regarding Rb-Sr, Sm-Nd, U-Th-Pb e Re-Os systematics in high-Ti basalts (Paranapanema and Pitanga) from northern PMP. In addition, the highly siderophile element concentrations, as well as 187Os/188Os isotope ratios, were measured in selected samples of low-Ti basalts (Esmeralda) from southern PMP. The geochemical and Sr-Nd-Pb isotope results of the present study are consistent with literature data, but refine the isotope variations (extreme) for the Paranapanema and Pitanga magma-types. These data, along with the concentrations of highly siderophile elements and Os isotope ratios suggest that the basalt mantle sources (asthenosphere or subcontinental lithospheric mantle) were affected by significant metasomatism (piroxenitic vein hybridization), related with old subduction and/or delamination processes.

We investigate the silicon (Si) cycle in the Southern Ocean through two isotopic approaches: (1) 30Si-incubation experiments and (2) natural silicon isotopic composition (ä30Si). 30Si-spiked incubation allows to discriminate the short-term (~ 1 day) net Si-uptake flux in bSiO2 production and dissolution. ä30Si of both biogenic silica and dissolved silicon integrates at seasonal/annual scale bSiO2 production or dissolution and mixing.<p>(1) A new mass spectrometer method (HR-SF-ICPMS) has been developed for 30Si-isotopic abundance measurements. This methodology is faster and easier than the previous available methodologies and has the same precision. A complete set of incubation was coupled with parallel 32Si-incubations and the two methodologies give not significantly different bSiO2 production rates. In the Southern Ocean, especially in the southern Antarctic Circumpolar Current, the large silicic acid concentration degrades the sensitivity of the method with Si dissolution fluxes staying generally below the detection limit. In contrast, the 28Si-isotopic dilution was sensitive enough to assess low biogenic silica dissolution rates in silicic acid poor waters of the northern ACC. We show that large accumulation of detrital dissolving biogenic silica after productive period implies really efficient silicon loop with integrated (euphotic layer) dissolution:production ratio equal or larger than 1.<p> (2) We largely expand the silicic acid isotopic data in the open ocean. Relatively simple mass and isotopic balances have been performed in the Antarctic Zone and have allowed to apply for the first time ä30Si in a quantitative way to estimate regional net silica production and quantify source waters fueling bSiO2 productivity. We observe that at the end of the productive period as suggested with 30Si-incubation, large accumulation of detrital biogenic silica in the surface waters increase the D:P ratio and subsequently dampens the bSiO2 production mediated isotopic fractionation with residual biogenic silica carrying heavier ä30Si than expected. Seasonal isotopic evolution is simulated and seems in agreement with our observations. These simulations strongly suggest working with non-zero order equations to fully assess the seasonal expression of the different processes involved: mixing, uptake, dissolution. Si-isotopes are also tracking the origin and fates of the different ACC pools across the Southern Ocean meridional circulation. Moreover during the circumpolar eastward pathway, the bSiO2 dissolution in deep water decreases the corresponding ä30Si values and this imprint is further transmitted via the upper limb of the meridional circulation in the intermediate water masses.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Indiana University-Purdue University Indianapolis (IUPUI) / Precipitation trends and their driving mechanisms are examined over a variety of spatial and temporal scales using a multi-proxy, decadally-resolved sediment record from Martin Lake that spans the last 2300 years. This unique archive from a northern Indiana kettle lake documents significant climate variability during the last 2 millennia and shows that the Midwest has experienced a wide range of precipitation regimes in the late Holocene. Three independent proxies (i.e., oxygen and carbon isotopes of authigenic carbonate and %lithics) record variations in synoptic, in-lake and watershed processes related to hydroclimate forcing, respectively. Together, these proxies reveal enhanced summer conditions, with a long period of water column stratification and enhanced summer rainfall from 450 to 1200 CE, a period of time that includes the so-called Medieval Climate Anomaly (950-1300 CE). During the Little Ice Age, from 1260 to 1800 CE, the three proxy records all indicate drought, with decreased summer rainfall and storm events along with decreased lake stratification. The Martin Lake multi-proxy record tracks other Midwest climate records that record water table levels and is out-of-phase with hydroclimate records of warm season precipitation from the High Plains and western United States. This reveals a potential warm season precipitation dipole between the Midwest and western United States that accounts for the spatial pattern of late Holocene drought variability (i.e., when the Midwest is dry, the High Plains and the western United States are wet, and vice versa). The spatiotemporal patterns of late Holocene North American droughts are consistent with hydroclimate anomalies associated with mean state changes in the Pacific North American teleconnection (PNA). Close associations between late Holocene North American hydroclimate and records of Northern Hemisphere temperatures and the Pacific Ocean-atmosphere system suggests a mechanistic linkage between these components of the global climate system that is in line with observational data and climate models. Based on our results, predominantly –PNA conditions and enhanced Midwestern summer precipitation events are likely to result from continued warming of the climate system. In the western United States, current drought conditions could represent the new mean hydroclimate state.

Les potentiels de nouveaux moyens d’investigation en sciences de l’environnement, tel que la géochimie des isotopes stables du Cu et du Zn et l’étude de la spéciation des éléments en trace métalliques (ETM) par titrage acidimétrique sont évalués dans le cadre de trois cas d’études, faisant intervenir des matériaux de matrices et de concentrations en ETM variables. Afin de mettre en évidence de très subtiles variations des compositions isotopiques du Cu et du Zn dans les matériaux particulaires variablement pollués, une attention particulière à été voué à la mise au point des méthodes de séparation chimique et d’analyse par MC-ICP-MS. La méthodologie analytique a été développée afin d’exploiter tout les avantages techniques offerts par le spectromètre de masse à l’ULB. Différents modes d’introduction (plasma humide vs plasma sec (Aridus/DSN), d’acquisition des mesures (mode statique ou dynamique) de correction du biais de masse (dopage au Cu, au Zn et au Ga; correction SSBM, SSBC et EEN)ont été évaluées, pour leurs effets sur la précision et la reproductibilité des mesures. D’autres travaux ont permis de quantifier les effets des interférences spectrales et non spectrales par les éléments de la matrice (Ti, Cr, Co,Fe, Ba, Si, Na, Mg et Ca)et par le rapport dopant/analyte en vue de comprendre les sources d’inexactitudes des mesures isotopiques et d’y remédier. Les données isotopiques acquises sur des minerais, sur des (plaques de) dépôts atmosphériques (usine Pb-Zn Metaleurop de Noyelles-Godault), sur des sédiments et des matières en suspension (estuaire de l’Escaut et mer du Nord), révèlent des variations significatives des compositions isotopiques du cuivre et du zinc. Dans l’estuaire de l’Escaut, les variations temporelles (carotte non perturbée, enregistrant la sédimentation sur 30 ans) et spatiales (matières en suspension échantillonnées sur 100 km, selon le profil de salinité) sont caractérisées par des signatures isotopiques en Zn anticorrélées à celle du Cu. Les données peuvent permettre de distinguer le fond géochimique naturel (le « réservoir naturel »), les pollutions diffuses (le « réservoir anthropique commun »- intégrant de multiples sources de contamination en provenance du bassin versant) et certaines pollutions ponctuelles associées à la métallurgie du Zn. Alors que les procédés utilisés en métallurgie sont eux,capable de produire des signatures isotopiques très fractionnées en Zn, ni la diagenèse précoce dans les sédiments, ni les gradients physicochimiques développés lors du mélange des eaux continentales et marines ne sont capables d’affecter significativement la signature isotopique du Cu et du Zn en phase particulaire. Dans de tels milieux, les signatures isotopiques en Cu et Zn (ainsi que celles en Pb) semblent n’être contrôlées que par le mélange conservatif entre le « réservoir naturel » et le « réservoir anthropique commun ». Les données en elles-mêmes constituent la seule base de données isotopiques en Cu, Zn, Pb dans des matériaux particulaires anthropisés estuariens et marins jamais produite à ce jour. Elles permettent de prédire que la signature isotopique en Cu du « réservoir naturel » devrait être légèrement plus enrichie en isotopes lourds que celle du réservoir « anthropique commun » (par analogie au Zn).<p>Si la géochimie isotopique du Cu et du Zn a le potentiel de distinguer différentes sources de pollution, l’évaluation des risques liés à ces pollutions doit tenir compte des formes chimiques des ETM, typiquement mises en évidences par les méthodes d’extraction sélectives (séquentielles, dont le protocole BCR). La méthode alternative proposée pour l’étude de la spéciation, plus versatile (capable de mettre en évidence des phases non prédéfinies et applicable à une variété de matrices plus large) est capable de surmonter plusieurs limitations (dont les problèmes de sélectivité liées au mauvais contrôle de l’acidité du milieu réactionnel) caractéristiques des méthodes traditionnelles. Appliquée à des sédiments marins/estuariens et des sols, la méthode de titrage acidimétrique s’est révélée capable de quantifier les proportions relatives des phases acido-solubles (principal problème des méthodes d’extraction sélectives), ce qui permet d’établir univoquement la spéciation des éléments qui leurs sont associés, d’évaluer la réactivité des ETM vis-à-vis du pH, mais aussi d’évaluer la sélectivité des protocoles d’extraction séquentielle « BCR » et « Tessier ». La méthode de titrage acidimétrique apporte également des informations importantes sur la géochimie des éléments majeurs dans l’estuaire de l’Escaut et met en évidence les particularités minéralogiques des sols pollués en comparaison aux sédiments.<p>Les études de cas démontrent que ces nouvelles techniques ont des applications dans le domaine de la géochimie de l’environnement, mais peuvent également être vouées, sur le moyen/long terme à une utilisation sortant du cadre des sciences exactes. En effet, l’identification/discrimination des sources de pollutions et l’évaluation des risques de remobilisation des polluants métalliques font partie des nombreuses questions posées par la société aux scientifiques de l’environnement. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished