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<p dir="ltr">To better predict volcanic behavior, we must understand the processes that occur in the underlying magma reservoirs. This thesis contains three chapters that work together to better understand processes that occur in sub-volcanic reservoirs. Chapter 2 is a study of an ancient, coupled volcanic-plutonic system to determine the link between the volcanic and plutonic parts of the system. The IXL-Job Canyon magmatic system is an ~28-29 Ma system, which shows a rapid transition between eruption of tuffs and lava flows to construction of an upper-crustal pluton, via incremental emplacement. The system experienced an eruptive hiatus during and after pluton construction, until the eruption of a newly identified, younger, rhyolitic tuff. This work suggests that the absence of volcanic activity at the surface does not mean that the underlying magmatic plumbing system is also inactive. Chapter 3 compiles existing U-Pb zircon ID-TIMS data for upper-crustal, silicic magmatic systems, to determine the size and frequency of magmatic increments that accumulate to build up these systems. A Monte Carlo-based model is used to investigate the underlying distributions of the increment size and time between increments, and results in sizes and inter-event times that follow an exponential distribution. This work helps guide how we can try to introduce broadly generalizable complexities into thermal models of such systems. Chapter 4 focuses on organic interferences, a common issue that impacts the speed and quality of U-Pb and Pb-Pb data collected on TIMS instruments. We share two techniques used at the Purdue Radiogenic Isotope Geology Lab to first reduce and then avoid any residual organic interferences. These techniques help shorten analytical times, increasing throughput, and provide a means to reduce uncertainties on our measurements, since the presence of organic interferences can bias and increase the uncertainties on U-Pb dates.</p>

Le gisement de Tocantinzinho est situé sur la province aurifère de Tapajós et est le plus grand gisement d'or de la province, avec 53,9 tonnes d'or estimées. Sa formation commence par un magmatisme granodioritique autour de 2005 Ma, suivi d'un magmatisme granitique. Le granite Tocantinzinho est composé de deux faciès principaux (syenogranite - 1996± 2Ma; monzogranite 1989±1 Ma), des corps d’aplite et de pegmatite, qui suggère un magmatisme enrichie en fluide et mis en place à faible profondeur. Intrusifs dans ces roches, des dykes d'andésite (1998±8Ma) ont des fragments de granite et des mélanges entre les 2 magmas suggèrent un magmatisme à la fois continu et polyphasé. Il est proposé que les premiers dykes d’andésite se sont mis en place alors que le granite n’était pas entièrement cristallisé (mingling) et les derniers lors des stades de déformation à l’état solide du granite. Utilisant la courbe de refroidissement, un âge minimum de 1975 Ma a été estimé pour l’andésite. Les taux de refroidissement des roches plutoniques varient de 3,6 à 14,7°C/Ma, avec une moyenne de 7,5°C/Ma, suggérant que les processus d'exhumation verticale sont faibles. La géométrie allongée du granite ainsi que la tectonique syn-magmatique de l'andésite corroborent la prédominance des mouvements horizontaux. L’affinité calc-alcaline fortement potassique et des anomalies en niobium définissent deux configurations possibles pour le cadre géotectonique: arc continental de type Andin ou Post-collisionnel. Compte tenue la relation génétique entre magmatisme, cisaillement décrochant et les faibles taux de refroidissement, l’environnement post-collisionnel est plus probable. Cela ensemble avec les âges nous permettent de comparer ces roches avec celles de la Suite Intrusive Creporizão (1997-1957Ma). La dacite (1992 ± 2 Ma) recoupe les autres roches, cependant, la signature géochimique comparable aux roches anorogéniques suggère qu’elle appartient à une série magmatique distinct. La zone minéralisée est limitée par deux failles majeures senestres de direction N100°-130E°. Le granite Tocantinzinho et les roches hypo-volcaniques déformées sont dans ce couloir, altérées par de fluides hydrothermaux et minéralisées pendant deux phases tectoniques distinctes. La première est caractérisée par des brèches et des microfractures remplies par muscovite (1864±5Ma) et pyrite, associées à de faibles teneur d’or (<1,5ppm) restreintes au granite. La deuxième phase a été contrôlée par le cisaillement décrochant senestre normal générant des fentes de tension et des brèches remplies par quartz, chlorite, calcite, albite, rutile, pyrite, galène, sphalérite, chalcopyrite et or. La teneur en or peut atteindre jusqu'à 70 ppm dans les veines riches en sulfures. Ces structures de remplissage syntectonique sont parallèles entre elles et orientées N30-60°E. Deux hypothèses ont été proposées pour expliquer la genèse du gisement: la première considère une relation génétique entre magmatisme et minéralisation au moins pour le premier stage de minéralisation selon un modèle porphyrique et la seconde alternative considère une réactivation des failles préexistantes par une tectonique transtensive liée au magmatisme Maloquinha (ca. 1880Ma) pour les deux stades minéralisateurs. Les deux phases dans les deux hypothèses, ont été classées comme des minéralisations de type magmato-hydrothermale qui pourraient être classées soit comme des systèmes d'or liés à l'intrusion. De nouveaux travaux sur le terrain et en laboratoire seraient nécessaires pour identifier et caractériser la nature et la source des fluides hydrothermaux, pour dater la minéralisation et mieux comprendre le rôle des roches hypo-volcaniques. Toutefois, les premiers résultats, et notamment le rôle fondamental du contrôle tectonique pour la minéralisation sont très significatifs et peuvent aider de manière conséquente à l'établissement des programmes d'exploration et d'exploitation futurs. / The Tocantinzinho deposit is located on the Tapajós Gold Province and is the largest gold deposit within Province, with 53,9 tons of gold. Its formation begins with a granodioritic magmatism around 2005Ma, followed by a granitic magmatism 10 Ma latter. The Tocantinzinho granite is composed by two main facies, syenogranite (1996±2Ma) and monzogranite (1989±1Ma), and by aplite and pegmatite bodies, suggesting a fluid-rich magmatism at shallow depth. Andesite dikes (1998±8Ma) are intrusive in both rocks. Sharp fragments of those rocks along contacts and minor mingling with granitic magma suggest a multiphase magmatism at distinct timing. The first dikes have intruded within granite when it was crystalizing, thus a minimum age of 1975Ma was estimated. Cooling rates of plutonic rocks vary from 3.6 to 14.7°C/Ma, with an average of 7.5°C/Ma, suggesting vertical exhumation processes were minor. The elongated geometry of granite along with sin-magmatic strike-slip tectonics of andesite corroborate the predominance of horizontal movements. Geochemical analysis show high-K calk-alkaline affinity and niobium anomaly indicator of two possible geotectonic settings for these rocks: Andean-type continental arc or post-collisional one. Considering the genetic relationship between magmatism, strike-slip faults, and low cooling rates, a post-collisional setting is more likely. The geochemical signature, ages and style of tectonism allow us to compare those rocks with the ones from Creporizão Intrusive Suite (1997-1957Ma). Dacite dikes (1992±2Ma) cut across all other rocks, but the temporal relationship among them remains misunderstood, due to the geochemical signature similar to the anorogenic rocks, suggesting it belongs to a distinct and latter magmatic series. Indeed, the dated zircons were probably inherited from host rocks. The mineralized area is restricted to a domain constrained by two major sinistral strike-slip N100°-130E°E faults that comprises the Tocantinzinho granite and sub-volcanic rocks, which were hydrothermally altered, brittle deformed and mineralized during two phases. The first one is characterized by breccias and microfractures infilled with muscovite (1864±5Ma) and pyrite, which contains low gold grades and are restricted to the Tocantinzinho granite. The second phase was controlled by strike-slip and normal tectonics generating tension gashes veins and pull apart breccias infilled with quartz, chlorite, calcite, albite, rutile, pyrite, galena, sphalerite, chalcopyrite, and gold. The gold grade can reach up to 70 ppm in some sulfide-rich veins. These structures are parallel and mainly trends N30-60°E, showing textures and orientated minerals typical of syn-tectonic infilling. Based on petrographical features and argon ages two hypothesis were proposed for the ore genesis: the first one consider a genetic relationship between magmatism and ore fluids for first mineralization stage and the second hypothesis consider a reactivation of pre-existing faults by an extensional tectonism related to the Maloquinha Intrusive Suite magmatism (ca.1880Ma) for this phase. The second mineralization phase is considered as formed as consequence of tectonic reactivation at ca. 1880Ma, in both hypothesis. Both phases in both hypothesis were classified as magmatic-hydrothermal ore mineralization and might be classified as intrusion-related gold systems. However, new field works are important in order to identify and characterize the nature and source of hydrothermal fluids, as well as ore dating and new geochemical and geochronological data of sub-volcanic rocks are imperative to better understand the genesis and evolution of the Tocantinzinho gold deposit. Such results, strongly linked to the fact that the tectonic control seem significant, may help for future exploration and exploitation programs.

Le Granite Passa Três est situé à l'Est de l'Etat du Paraná, au Sud du Brésil, et est allongé selon une direction NNE-SSW. Sa mise en place se fait au cœur des metapélites mesoprotérozoïques du Groupe Açungui (Province Mantiqueira). La minéralisation d’or du Granite Passa Três est composée par des veines de quartz contenant des quantités variables de fluorite, sulfures et carbonates. Les objectifs principaux de ce travail de thèse sont : de comprendre le modèle de formation du système de veines minéralisées en prenant en compte les relations entre magmatisme, hydrothermalisme, déformation et minéralogie à la fois dans l’espace et dans le temps ; la caractérisation de la nature, de la source et des conditions de dépôt des fluides ; et la caractérisation du modèle métallogénique de ce gisement singulier. Pour arriver à ces objectifs, les méthodes utilisées seront, en sus de la géologie structurale et de terrain : la pétrographie, la géochronologie U-Pb (LA-ICP-MS) sur zircon et 40Ar-39Ar sur muscovite, la microscopie électronique à balayage (MEB), la microsonde électronique, la fluorescence X (XFR), l’analyse isotopique du soufre (δ34S) et l’analyse microthermométrique et RAMAN des inclusions fluides. Les données structurales ont montré la coexistence de deux systèmes principaux de filons minéralisés, l’un N-S et l’autre E-W, avec des pendages de 60-75°W et 45-70°S, respectivement. Les deux systèmes sont interprétés comme contemporains et conjugués. Les corps minéralisés forment des géométries sigmoïdales qui résultent de l’ouverture en pull-aparts résultant de mouvements en faille normale le long de plans de glissement à faible pendage. Le fort pendage des structures minéralisées s’explique par l’enveloppe globale formée par la succession des pull-aparts. Quatre étapes minéralogiques sont à l’origine de la formation du système minéralisé : phase 1 [qtz 1 + fl], phase 2a [qtz 2 + py 2a ± or ± cpy ± aik ± fl ± sph ± musc], phase 2b [qtz 2 + py 2b + or + cpy + aik + ank ± sph ± fl ± musc] et phase 3 [qtz 3 + ank + calc + molyb ± aik ± musc ± fl]. L’or se trouve dans la forme d’or invisible et d’or natif dans des fractures qui affectent les pyrites des phases 2a et b, systématiquement associé avec la chalcopyrite et l’aikinite. L’altération associée à la minéralisation inclue des assemblages composés par muscovite/quartz/pyrite (altération du type greisen) et séricite/carbonate/clinochlore (altération phyllique). Les valeurs δ34S des pyrites (de -0.1‰ à 1.1‰) indiquant que le soufre du dépôt peut être d’origine magmatique. Cette hypothèse est en accord avec l’observation systématique, dans les parties supérieures du granite (sondage et niveaux supérieurs de la mine), de structures caractéristiques de transition magmatique-hydrothermale comme des systèmes aplo-pegmatitiques, des veines de quartz à bordure de K-feldspath, des concentrations de quartz de type stockscheider et des textures de solidification unilatérales (UST). Les résultats de géochronologie confirment cette hypothèse avec des âges U-Pb sur zircon (611.9±4.7 et 611.9±5.6 Ma pour le granite à grain moyen (GEM) et le microgranite (GEF) et 40Ar-39Ar sur muscovite (veines à bordure de K-feldspath : 612.9±2 à 608.8±2 Ma ; veines minéralisées : 611.7±2 à 608.8±2 Ma ; veines de quartz précoces : 608.4±2 Ma) très proches. Ces âges obtenus indiquent que la mise-en-place du granite, l’exsolution du fluide magmatique-hydrothermal et la formation des veines de quartz aurifères ont été réalisées pendant un écart de temps de 5 Ma, entre 613 et 608 Ma. La minéralisation (611 à 608 Ma) contemporaine de la cristallisation du granite (612 à 610 Ma), l’association de l’or avec des minéraux de bismuth (aikinite), la démonstration du contrôle structural sur la formation des veines et les évidences de transition magmatique-hydrothermale en domaine de coupole granitique montrent que le dépôt d’or du Granite Passa Três partage plusieurs similitudes avec les dépôts du type intrusion-related. / The Passa Três Granite is situated in southern Brazil (Paraná State) and presents a NNE-SSW elongated shape. This intrusion is emplaced within metapelites of the Mesoproterozoic Açungui Group (Ribeira Belt, Mantiqueira Province), between the N40E trending Morro Agudo and Lancinha faults. Gold mineralisation is composed of centimetric to metric quartz veins with fluorite, sulphides and carbonates. The main objectives of this work are i) to understand the model of formation of the mineralised veins systems taking into account the relationships between magmatism, hydrothermalism, deformation and mineralogy in space and time; ii) the characterization of the nature, source and emplacement conditions of the ore fluids; and iii) the characterization of a metallogenic model for this singular deposit. In order to reach these purposes, the methods to be applied include, beyond the structural geology and field works: petrography, U-Pb zircon (LA-ICP-MS) and 40Ar-39Ar muscovite geochronology, scanning electron microscopy (SEM), electron-microprobe analyses (EPMA), X-ray fluorescence (XRF), isotopic analysis of sulphur (δ34S), and microthermometric and Raman analysis of fluid inclusions. Structural data showed the coexistence of two major normal mineralised vein systems, one N-S and the other one E-W, with dips of 60-75ºW and 45-70ºS, respectively. Both systems are interpreted to be contemporaneous and conjugated. Orebodies form sigmoidal geometries that resulted of the opening of pull-aparts as a consequence of the normal movements along low-angle fault planes. High-angle dip of the global mineralised structures is explained by the succession of the pull-aparts. Four mineralogical stages resulted in the formation of the mineralised system: phase 1 [quartz 1 + fluorite], phase 2a [quartz 2 + pyrite 2a ± gold ± chalcopyrite ± aikinite ± fluorite ± sphalerite ± muscovite], phase 2b [quartz 2 + pyrite 2b + gold + chalcopyrite + aikinite + ankerite ± sphalerite ± fluorite ± muscovite] and phase 3 [quartz 3 + ankerite + calcite + molybdenite ± aikinite ± muscovite ± fluorite]. Gold occurs as invisible gold and as native grains within fractures that affect pyrite 2a and 2b, commonly associated with chalcopyrite and aikinite. Alteration related to the mineralisation includes muscovite/quartz/pyrite (greisen type alteration) and sericite/carbonato/clinochlore (phyllic alteration) assemblages. The δ34S values of pyrite crystals (from -0.1‰ to 1.1‰) indicate that the sulphur in this deposit may have a magmatic origin. This hypothesis agrees with the systematic observation, within the upper part of the granite (drill holes and superior levels of the mine), of structures typical of magmatic-hydrothermal transition such as aplite-pegmatite systems, quartz veins with K-feldspar border, quartz concentration of stockscheider type and unilateral solidification textures (UST). Geochronological data confirm this hypothesis with U-Pb zircon ages (611.9±4.7 and 611.9±5.6 Ma for medium grained granite facies (GEM) and microgranite (GEF), respectively) and 40Ar-39Ar muscovite dating (veins with K-feldspar border: 612.9±2 to 608.8±2 Ma; mineralised veins: 611.7±2 to 608.8±2 Ma; barren vein: 608.4±2 Ma), that are very close. These ages indicate that the granite emplacement, the magmatic-hydrothermal fluid release and the formation of gold-bearing quartz veins occur during a time lapse of approximately 5 Ma, between 613 and 608 Ma. The mineralisation (611 to 608 Ma) coeval to granite crystallization (612 to 610 Ma), the association of gold with Bi minerals (aikinite), the strong structural control for veins and magmatic-hydrothermal transition features at the roof of a small granitic intrusion suggest that the Passa Três gold deposit shares several similarities with intrusion-related gold deposits.

Foram determinadas as concentrações de terras raras (La, Ce, Nd, Sm, Eu, Tb, Yb e Lu) e outros elementos-traço (Cs, Rb, Ba, U, Th, Ta, Hf, Co e Sc) em 51 amostras representativas de derrames e soleiras das regiões norte e nordeste da Província Magmática do Paraná, que ocorrem no norte do estado de São Paulo e no sul de Minas Gerais. O método utilizado para estas determinações foi a técnica de ativação com nêutrons térmicos e epitérmicos, seguida de espectrometria gama de alta resolução, que forneceu resultados com elevados níveis de precisão e de exatidão (geralmente com valores inferiores a 10%), conforme atestado pelas concentrações determinadas no material geológico de referência JB-1. Os dados obtidos foram analisados conjuntamente com determinações de elementos maiores, menores e dos traços Sr, Y, Zr, Nb, Cr e Ni, realizadas por fluorescência de raios ? X. As rochas investigadas são quimicamente representadas por basaltos toleíticos, andesi-basaltos toleíticos e lati-basaltos, enquanto as mais evoluídas (MgO < 3%), que ocorrem de modo muito subordinado, são representadas por latitos e lati-andesitos, além de um riodacito. As rochas básicas (SiO2 < 55% e/ou MgO > 3%) são caracterizadas por apresentarem conteúdos de TiO2 maiores que 3%, sendo que grande maioria possui fortes semelhanças com os magmas-tipo Pitanga, embora tenham sido encontrados alguns derrames, localizados no norte do estado de São Paulo, geoquimicamente semelhantes aos magmas-tipo Urubici (típicos do sul da província). Rochas básicas com concentrações de TiO2 entre 2% e 3% foram também raramente encontradas, as quais representam equivalentes intrusivos de derrames Paranapanema. As rochas mais evoluídas só foram encontradas em soleiras e possuem características geoquímicas que indicam diferenciação a partir de magmas do tipo Pitanga. O comportamento de elementos maiores, menores e traços nas rochas intrusivas e extrusivas do tipo Pitanga, incluindo as mais diferenciadas, é compatível com um processo de evolução por cristalização fracionada envolvendo plagioclásios, clinopiroxênios e titano-magnetitas. A comparação entre derrames e soleiras do tipo Pitanga indica a atuação significativa de processos de diferenciação in situ nas rochas intrusivas, que causaram uma maior variabilidade composicional (soleiras: MgO entre 2,3% e 6,4%; derrames: MgO entre 3,2% e 5,5%). As rochas mais diferenciadas são também caracterizadas por anomalias positivas de európio, que sugerem o acúmulo de plagioclásio devido a esse processo de fracionamento. Os dados obtidos também reforçam que não houve participação significativa de componentes astenosféricos do tipo N-MORB, E-MORB e OIB na gênese das rochas básicas investigadas, as quais possuem grande similaridade geoquímica com os basaltos da Cadeia Rio Grande (sítio 516F) e Cadeia Walvis (sítio 525A), especialmente com os desta última, indicando o envolvimento do componente mantélico EMI. / It is presented the determination of rare earth (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) and other trace (Cs, Rb, Ba, U, Th, Ta, Hf, Co and Sc) element concentrations in 51 representative samples of flows and sills from northern and northeastern Paraná Magmatic Province, particularly those located at north of São Paulo State and south of Minas Gerais. The employed analytical method to those determinations was thermal and epithermal neutron activation analysis, followed by high resolution gamma ray spectrometry, which provided high precision and accuracy results (in general better than 10%), as verified by determinations in the international geological reference material JB-1. The obtained results were integrated with major, minor and trace (Sr, Y, Zr, Nb, Cr and Ni) elements determined by X-ray fluorescence. The investigated rocks are mainly represented by tholeiitic basalts, tholeiitic andesi-basalts and lati-basalts, with subordinate relatively evolved (MgO < 3wt%) lithotypes, which are represented by latites and lati-andesites, besides one rhyodacite. The basic rocks (SiO2 < 55% and/or MgO > 3%) are characterized by presenting TiO2 contents higher than 3wt%, very similar to Pitanga magma-type, although some flows, located at northern São Paulo State, geochemically similar to Urubici magma-type (typical of southern Paraná) were also found. Basic rocks having TiO2 contents between 2 and 3 wt% were rarely encountered and represent intrusive equivalents of Paranapanema flows. The more evolved rocks were just found in sills and have geochemical characteristics that indicate differentiation from Pitanga magma-types. Major, minor and trace element behaviour of intrusive and extrusive rocks of Pitanga type, including those differentiated ones, is compatible with evolution by fractional crystallization of plagioclases, clinopyroxenes and titanium magnetites. The comparison between flows and sills of Pitanga type indicates the significant role of in situ differentiation in the genesis intrusive rocks, causing its larger compositional variability (sills: MgO between 2.3 and 6.4wt%; flows: MgO between 3.2 and 5.5wt%). The most evolved rocks are also characterized by positive europium anomalies, which suggest plagioclase accumulation caused by such fractionation process. The obtained data also corroborate the lack of significant participation of N-MORB, E-MORB and OIB asthenospheric mantle components in the genesis of basic rocks, which present very close geochemical similarity with Rio Grande Rise (site 516F) and Walvis Ridge (site 525A) basalts, particularly with the last ones, indicating the involvement of EMI mantle component.

Os diques da Região dos Lagos, localizados entre os municípios de Arraial do Cabo, Cabo Frio e Armação dos Búzios (RJ), integram o Enxame de Diques da Serra do Mar (ESM) e apresentam particularidades geoquímicas e geocronológicas que fazem com que seu papel na abertura do Atlântico Sul ainda seja pouco compreendido. Este estudo apresenta os resultados da investigação detalhada sobre a gênese e a idade dessas intrusões, através novas análises de elementos maiores, menores, traços, razões isotópicas (Sr, Nd e Pb) e datações 40Ar/39Ar. Os diques são quimicamente representados por basaltos toleíticos, andesibasaltos toleíticos e basaltos transicionais, com teores de TiO2, em sua maioria, inferiores a 2% (BTi). Os dados de geoquímica elemental permitem identificar dois grupos, um mais primitivo e empobrecido em elementos incompatíveis (grupo A), e outro mais evoluído e enriquecido nesses elementos (grupo B). Os dados sugerem pouca ou nenhuma influência de contaminação crustal durante a evolução e apontam semelhanças do grupo A com os basaltos BTi (Esmeralda) da Província Magmática do Paraná (PMP). O grupo B, por sua vez, apresenta características distintas dos derrames BTi da PMP. O grupo A possui composições isotópicas pouco radiogênicas em Sr e mais radiogênicas em Pb que o grupo B, assemelhando-se àquelas dos diques Horingbaai da Namíbia. As razões isotópicas de Pb sugerem que os dois grupos foram originados por fontes mantélicas distintas, as quais são também menos radiogênicas que os derrames BTi da PMP. Os dados não se adequam à diferenciação por cristalização fracionada com assimilação concomitante ou por mistura envolvendo os reservatórios mantélicos clássicos. Este comportamento pode estar relacionado a heterogeneidades do manto litosférico, causadas por longos processos de subducção durante a amalgamação do Gondwana ocidental. As análises 40Ar/39Ar mostram que a presença de sericitização e albitização nos plagioclásios pode imprimir as idades desses processos nos espectros. Plagioclásios sericitizados do grupo A forneceram idades de 106-108 Ma, e também um provável evento de albitização em 96 Ma. Tais idades discordam tanto das de plagioclásios frescos (idades máximas de 125-140 Ma), afetados por excesso de Ar em decorrência de inclusões de piroxênio e apatita, como daquelas de 132 Ma obtidas em anfibólio-biotita. Estas últimas devem marcar a intrusão dos diques do grupo A, confirmando sua associação com a PMP. A análise em rocha total de um dique do grupo B apresentou idade máxima de cerca de 108 Ma, sugerindo que a intrusão dos grupos A e B podem não ser contemporâneas. A similaridade entre a idade do grupo B e aquela de soerguimento da costa sudeste sugere que estes diques possam ter sido originados durante esse evento, que também teria causado a alteração (sericitização) dos plagioclásios do grupo A. / The Região dos Lagos tholeiitic dykes, located in Rio de Janeiro State, encompass the Arraial do Cabo, Cabo Frio and Armação de Búzios towns and integrate the Serra do Mar Dyke Swarm. Their role in the South Atlantic opening processes is still poorly defined because of their peculiar geochemical and geochronological features. In this work, the petrogenesis and the geochronology of these intrusions were investigated in detail based on new data of elemental (major, minor and trace elements) and isotope (Sr, Nd and Pb) geochemistry along with a careful 40Ar/39Ar dating. The dykes are chemically represented by tholeiitic basalts, andesi tholeiitic basalts and transitional basalts, usually presenting TiO2 contents lower than 2% (LTi). The elemental geochemistry allows the recognition of two magmatic groups; one of them is more primitive and depleted in incompatible elements (group A), whereas the other one is more evolved and enriched in these elements (group B). The data also indicate that crustal assimilation, if existed, had a small role in the magmatic evolution of both groups, and point out similarities between group A and the LTi flows (Esmeralda) from the Paraná Magmatic Province (PMP). Group B, in turn, displays geochemical features very different from those of the LTi basalts from PMP. The Sr isotope compositions of group A are less radiogenic than those of the B one, but the opposite occurs with Pb, which makes the first group similar to the Horingbaai dykes from Namibia. The Pb isotope ratios indicate that A and B were originated from distinct mantle sources, which also differ from those related to PMP LTi flows. The isotope data are not compatible with assimilation-fractional crystallization processes or simple mixtures involving the classic mantle reservoirs. This behavior suggests origin in heterogeneous lithospheric subcontinental mantle, probably affected by long subduction periods during Western Gondwana amalgamation. The 40Ar/39Ar geochronological data point out that the presence of plagioclase sericitization and albitization in their rims may imprint the age of these events in the age spectra. Sericitized plagioclase grains of group A displayed ages of 106-108 Ma, while the albitized fractions provided ages of 96 Ma. Such results disagree with both the fresh plagioclase grains (maximum ages of 125-140 Ma), very affected by excess Ar due to pyroxene and apatite inclusions, and the 132 Ma age of the amphibole-biotite aliquots. This last result very probably corresponds to the dyke emplacement event, confirming the genetic relationship between group A and the PMP. Whole rock dating in a sericite-free group B dyke provided maximum age of 108 Ma, which would imply that A and B groups are not coeval. The similarity between the last age and the uplifting event of Southwestern Brazilian coast suggests that the dykes of group B could have been generated during such process, which also altered (sericitized) the plagioclases of the group A dykes.

Este trabalho apresenta a caracterização geoquímica e isotópica (Sr-Nd-Pb) das rochas subalcalinas diferenciadas dos diques do Enxame da Serra do Mar (ESM), localizado na costa dos estados de São Paulo e Rio de Janeiro, sendo constituído principalmente por diques básicos com altos teores de TiO2 (>3%). Os diques intermediários e ácidos, encontrados apenas na Ilha de São Sebastião e costa adjacente, foram submetidos à análise de elementos traços por ativação com nêutrons (AAN), que possibilitou a determinação de elementos terras raras (La, Ce, Nd, Sm, Eu, Tb, Yb e Lu) e outros traços incompatíveis (U, Th, Hf, Ta, Ba e Rb), além de Co e Sc. As amostras foram também analisadas por espectrometria de massa com plasma indutivamente acoplado (ICP-MS), que permitiu efetuar uma comparação entre os resultados obtidos pelos dois métodos. Foram ainda determinadas as razões isotópicas de Sr, Nd e Pb em cinco amostras representativas. Os dados obtidos por AAN indicam precisão de até 14% (maioria abaixo de 10%) e exatidão de até 4%. A comparação estatística dos dados de AAN com ICP-MS mostrou que as técnicas fornecem resultados estatisticamente concordantes para a grande maioria dos elementos analisados. Os diques diferenciados são quimicamente representados por lati-andesitos (LTA), dacitos (DAC) e riodacitos (RC). Dentre os LTA observa-se um conjunto de 4 amostras (Grupo 1) com características geoquímicas semelhantes às rochas basálticas Pitanga da Província Magmática do Paraná (PMP), embora apresentem razões isotópicas iniciais de Sr e Pb mais radiogênicas. Os demais LTA (Grupo 2) apresentam enriquecimento significativo de elementos fortemente incompatíveis. Entre as rochas mais diferenciadas dos LTA (Grupo 2) e aquelas dos DAC e RC há lacunas composicionais, sugerindo que a evolução não ocorreu por cristalização fracionada. À semelhança da gênese das rochas vulcânicas ácidas do tipo Chapecó-Ourinhos da PMP, é possível que os diques DAC e RC tenham sido originados por refusão de material de composição basáltica aprisionado na descontinuidade crosta-manto. As razões isotópicas dos diques do ESM sugerem que a gênese desse material basáltico envolveu fusão de manto litosférico subcontinental metassomatizado, conforme proposto para os diques mesozoicos do Espinhaço Meridional (Craton do São Francisco), que possuem composições isotópicas similares. Os magmas diferenciados gerados nesse processo podem ter sofrido contaminação crustal, conforme indicado também pelas composições isotópicas de Sr, Nd e Pb, requerendo, no entanto, um contaminante com características muito específicas. / The geochemical and isotopic (Sr-Nd-Pb) characterization of the subalkaline differentiated dykes from the Serra do Mar Swarm (ESM) is presented. These rocks are located at the coast of São Paulo and Rio de Janeiro states and are mainly composed by basic dikes with high contents of TiO2 (> 3%). Intermediate and acid dykes, which are found only in the São Sebastião Island and adjacent coast area were investigated by using neutron activation analysis (AAN), allowing determination of the concentrations of rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) and other compatible (Co and Sc) and incompatible trace elements (U, Th, Hf, Ta, Ba and Rb). The samples were also analyzed by mass spectrometry with inductively coupled plasma (ICP-MS), permitting the comparison between the results obtained by the two methods. The isotope compositions of Sr, Nd and Pb were also determined in five representative samples. The data obtained by AAN indicate precision of up to 14% (most below 10%) and accuracy of up to 4%. The statistical comparison of AAN and ICP-MS data showed that the techniques provide statistically identical results for the vast majority of the analyzed elements. The differentiated dykes are chemically represented by lati-andesites (LTA), dacites (DAC) and riodacites (RC). Four LTA samples (Group 1) have geochemical similarities with Pitanga basaltic flows from Paraná Magmatic Province (PMP), although presenting Sr and Pb initial ratios slightly more radiogenic. The remaining LTA (Group 2) rocks are enriched in highly incompatible trace elements. The compositional gap between the most evolved LTA (Group 2) and the DAC and RC suggests that the evolution of this rocks is not compatible with fractional crystallization processes. Likewise the genesis of Chapecó-Ourinhos acid volcanic rocks from PMP, it is possible that the DAC and RC have been generated by melting of basalt material, which was trapped in crust-mantle discontinuity. The isotope ratios of the ESM dykes suggest that this basaltic material was generated by melting of a metasomatized subcontinental lithospheric mantle source, due to ancient subduction processes, as proposed for the Mesozoic dykes from the Espinhaço Meridional (São Francisco Craton), whose isotope ratios are very similar. The differentiated magmas generated in this process would be affected by crustal contamination during their ascension, as also indicated by the Sr, Nd and Pb isotope compositions, requiring however, very specific characteristics for the contaminant.

Foi desenvolvido um programa computacional escrito na linguagem de programação C++ denominado CALFRAC para quantificar o processo de cristalização fracionada em sistemas ígneos, utilizando para isso as concentrações dos elementos maiores, menores e traços. O algoritmo moderniza, torna mais eficiente e aprimora os programas publicados na literatura e possui a grande vantagem de poder calcular, automaticamente, todas as possíveis combinações de evolução das amostras envolvidas na diferenciação, além de associar aos cálculos os elementos-traço, os quais servem para confirmar os resultados sugeridos pelos ajustes dos elementos maiores e menores. O CALFRAC calcula a fração total subtraída do magma inicial e as frações referentes a cada mineral fracionado através do cálculo do balanço de massa, utilizando as concentrações de elementos maiores e menores, empregando os métodos de estimativa de máxima verossimilhança e dos multiplicadores de Lagrange para a resolução por mínimos quadrados, enquanto para os elementos-traço o programa utiliza a Equação de Rayleigh. Em ambos os casos a média dos erros percentuais relativos é usada como indicação das melhores evoluções. O programa CALFRAC foi aplicado na investigação da possibilidade de diferenciação por cristalização fracionada em amostras de soleiras de diabásio da Bacia do Paraná, que ocorrem nos municípios de Salto do Itararé, Ponta Grossa, Prudentópolis, Rebouças, Irati, Reserva e Jaguariaíva (PR), as quais foram coletadas para essa finalidade. Nas 33 amostras coletadas foram realizadas determinações de elementos maiores, menores e traços, incluindo terras raras, empregando-se os métodos de Fluorescência de Raios X e Ativação Neutrônica. Os resultados fornecidos pelo programa foram insatisfatórios, não sendo possível estabelecer um percurso de diferenciação das rochas mais primitivas para as mais diferenciadas das intrusões, devido ao fato de que provavelmente muitas das amostras analisadas representam a mistura de magmas com porções contendo acumulação de fases minerais causada pelo próprio processo de cristalização fracionada in situ. / CALFRAC is a computer program written in C++ programming language developed to quantify fractional crystallization processes in igneous systems. Major, minor and trace element concentrations are used as input for calculations. The new algorithm enhances and makes the program more efficient than those published in the literature. Besides it is capable to automatically calculating all possible rock sample combinations involving differentiation by fractional crystallization process, using in addition trace element concentrations to corroborate the results obtained by the fitting of major and minor element abundances. CALFRAC calculates the total fraction subtracted from the original magma and the percentage of each fractionated mineral by solving least-squares mass balance equations based on major and minor element concentrations. The methods of maximum likelihood estimate and Lagrange multipliers are used to solve the equations, whereas for the quantification of trace elements the program uses the Rayleigh Equation. In both cases the mean relative percentage errors is used as an indication of the best results. The program CALFRAC was applied to investigate the possibility of differentiation by fractional crystallization of diabase samples from Paraná Basin sills, which outcrop nearby Salto do Itararé, Ponta Grossa, Prudentópolis, Rebouças, Irati, Reserva and Jaguariaíva towns (PR). The 33 collected samples were analyzed for major, minor and trace elements, including rare earths, employing X-Ray Fluorescence and Neutron Activation methods. The program output was not satisfactory, since it was not possible to establish a differentiation sequence from the more primitive to the more differentiated rocks of the intrusions. This is probably due to the fact that many rock samples are the result of mixing of magmatic melts with mineral accumulation zones, which were formed by the in situ fractional crystallization process.

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.

Este trabalho apresenta a caracterização geoquímica e isotópica (Sr-Nd-Pb) das rochas subalcalinas diferenciadas dos diques do Enxame da Serra do Mar (ESM), localizado na costa dos estados de São Paulo e Rio de Janeiro, sendo constituído principalmente por diques básicos com altos teores de TiO2 (>3%). Os diques intermediários e ácidos, encontrados apenas na Ilha de São Sebastião e costa adjacente, foram submetidos à análise de elementos traços por ativação com nêutrons (AAN), que possibilitou a determinação de elementos terras raras (La, Ce, Nd, Sm, Eu, Tb, Yb e Lu) e outros traços incompatíveis (U, Th, Hf, Ta, Ba e Rb), além de Co e Sc. As amostras foram também analisadas por espectrometria de massa com plasma indutivamente acoplado (ICP-MS), que permitiu efetuar uma comparação entre os resultados obtidos pelos dois métodos. Foram ainda determinadas as razões isotópicas de Sr, Nd e Pb em cinco amostras representativas. Os dados obtidos por AAN indicam precisão de até 14% (maioria abaixo de 10%) e exatidão de até 4%. A comparação estatística dos dados de AAN com ICP-MS mostrou que as técnicas fornecem resultados estatisticamente concordantes para a grande maioria dos elementos analisados. Os diques diferenciados são quimicamente representados por lati-andesitos (LTA), dacitos (DAC) e riodacitos (RC). Dentre os LTA observa-se um conjunto de 4 amostras (Grupo 1) com características geoquímicas semelhantes às rochas basálticas Pitanga da Província Magmática do Paraná (PMP), embora apresentem razões isotópicas iniciais de Sr e Pb mais radiogênicas. Os demais LTA (Grupo 2) apresentam enriquecimento significativo de elementos fortemente incompatíveis. Entre as rochas mais diferenciadas dos LTA (Grupo 2) e aquelas dos DAC e RC há lacunas composicionais, sugerindo que a evolução não ocorreu por cristalização fracionada. À semelhança da gênese das rochas vulcânicas ácidas do tipo Chapecó-Ourinhos da PMP, é possível que os diques DAC e RC tenham sido originados por refusão de material de composição basáltica aprisionado na descontinuidade crosta-manto. As razões isotópicas dos diques do ESM sugerem que a gênese desse material basáltico envolveu fusão de manto litosférico subcontinental metassomatizado, conforme proposto para os diques mesozoicos do Espinhaço Meridional (Craton do São Francisco), que possuem composições isotópicas similares. Os magmas diferenciados gerados nesse processo podem ter sofrido contaminação crustal, conforme indicado também pelas composições isotópicas de Sr, Nd e Pb, requerendo, no entanto, um contaminante com características muito específicas. / The geochemical and isotopic (Sr-Nd-Pb) characterization of the subalkaline differentiated dykes from the Serra do Mar Swarm (ESM) is presented. These rocks are located at the coast of São Paulo and Rio de Janeiro states and are mainly composed by basic dikes with high contents of TiO2 (> 3%). Intermediate and acid dykes, which are found only in the São Sebastião Island and adjacent coast area were investigated by using neutron activation analysis (AAN), allowing determination of the concentrations of rare earth elements (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) and other compatible (Co and Sc) and incompatible trace elements (U, Th, Hf, Ta, Ba and Rb). The samples were also analyzed by mass spectrometry with inductively coupled plasma (ICP-MS), permitting the comparison between the results obtained by the two methods. The isotope compositions of Sr, Nd and Pb were also determined in five representative samples. The data obtained by AAN indicate precision of up to 14% (most below 10%) and accuracy of up to 4%. The statistical comparison of AAN and ICP-MS data showed that the techniques provide statistically identical results for the vast majority of the analyzed elements. The differentiated dykes are chemically represented by lati-andesites (LTA), dacites (DAC) and riodacites (RC). Four LTA samples (Group 1) have geochemical similarities with Pitanga basaltic flows from Paraná Magmatic Province (PMP), although presenting Sr and Pb initial ratios slightly more radiogenic. The remaining LTA (Group 2) rocks are enriched in highly incompatible trace elements. The compositional gap between the most evolved LTA (Group 2) and the DAC and RC suggests that the evolution of this rocks is not compatible with fractional crystallization processes. Likewise the genesis of Chapecó-Ourinhos acid volcanic rocks from PMP, it is possible that the DAC and RC have been generated by melting of basalt material, which was trapped in crust-mantle discontinuity. The isotope ratios of the ESM dykes suggest that this basaltic material was generated by melting of a metasomatized subcontinental lithospheric mantle source, due to ancient subduction processes, as proposed for the Mesozoic dykes from the Espinhaço Meridional (São Francisco Craton), whose isotope ratios are very similar. The differentiated magmas generated in this process would be affected by crustal contamination during their ascension, as also indicated by the Sr, Nd and Pb isotope compositions, requiring however, very specific characteristics for the contaminant.