Theoretical investigation of electronic and optical properties of andalusite within density functional theory

The electronic and optical properties of andalusite were studied by using quantum-mechanical calculations based on the density functional theory (DFT). The electronic structure shows that andalusite has a direct band gap of 5.01 eV. The complex dielectric function and optical constants, such as extinction coefficient, refractive index, reflectivity and energy-loss spectrum, are calculated. The optical properties of andalusite are discussed based on the band structure calculations. It is shown that the O-2p states and Al-3s states play a major role in optical transitions as initial and final states, respectively. (C) 2010 Elsevier Ltd. All rights reserved.

Electron paramagnetic resonance and the thermoluminescence emission mechanism of the 280 degrees C peak in natural andalusite crystal

Samples of natural andalusite (Al(2)SiO(5)) crystal have been investigated in terms of thermoluminescence (TL) and electron paramagnetic resonance (EPR) measurements. The TL glow curves of samples previously annealed at 600 degrees C for 30 min and subsequently gamma-irradiated gave rise to four glow peaks at 150, 210, 280 and 350 degrees C. The EPR spectra of natural samples heat-treated at 600 degrees C for 30 min show signals at g = 5.94 and 2.014 that do not change after gamma irradiation and thermal treatments. However, it was observed that the appearance of a paramagnetic center at g=1.882 for the samples annealed at 600 degrees C for 30 min followed gamma irradiation. This line was attributed to Ti(3+) centers. The EPR signals observed at g=5.94 and 2.014 are due to Fe(3+). Correlations between EPR and TL results of these crystals show that the EPR line at g=1.882 and the TL peak at 280 degrees C can be attributed to the same defect center. (C) 2011 Elsevier B.V. All rights reserved.

Metodologias para a qualificação de águas minerais naturais e águas de nascente

Dissertação de mestrado em Ordenamento e Valorização de Recursos Geológicos

Melt topology and chemistry during partial melting in contact aureoles : an experimental study and field example

This study was initiated to investigate partial melting within the high-grade metamorphic rocks beneath the Little Cottonwood contact aureole (Utah, USA), in order to understand the melt generation, melt migration, and geometry of initial melt distribution on grain scale during crustal anatexis. The emplacement of the Little Cottonwood stock produced a contact aureole in the pelitic host rocks of the Big Cottonwood formation (BC). Metamorphic isogrades in pelitic rocks range form biotite to 2nd sillimanite grade as a function of distance from the contact. Migmatites are restricted to the highest grade and resulted form partial melting of the BC formation rocks. First melt was produced by a combined muscovite/biotite dehydration reaction in the sillimanite + k-feldspar stability field. Melt extraction from the pelites resulted in restites (magnetite + cordierite + alumosilicate ± biotite) surrounded by feldspar enriched quartzite zones. This texture is the result of gradual infiltration of partial melts into the quartzite. Larger, discrete melt accumulation occurred in extensional or transpressional domains such as boudin necks, veins, and ductile shear zones. Melt composition are Si02- rich, crystallized as pegmatites, and apparently were very mobile. They were able to infiltrate the quartzite pervaisivly. These melts are similar in composition to first melts produced in the hydrothermal partial melt experiments at 2kbar between 700 - 800°C on fine grained high metamorphic rocks (andalusite-cordierited-biotite-zone) of the BC formation. The experimental melts are water rich and in disequilibrium with the melting rock. Initial melt composition is heterogeneous for short run duration, reflective a lack of chemical equilibrium between individual melt pools. Rock core scale heterogeneity decreased with time indicating partial homogenization of melt compositions. A simultaneous shift of melt composition to higher silica content with time was observed. The silica content of the melt increased due to local melt/mineral reactions. Melt textures indicate that reactive melt transport is most efficient along grain boundaries rimmed by dissimilar grains. Melt heterogeneity resulted in chemical potential gradients which are major driving forces for initial melt migration and govern melt distribution during initial melting. An additional subject of the thesis is the crystal size distributions of opaque minerals in a fine-grained, high-grade meta-pelite of the Big Cottonwood which were obtained from 3D X-ray tomography (uCT) and 2D thin section analysis. µCT delivers accurate size distributions within a restricted range (~ a factor of 20 in size in a single 3D image), while the absolute number of crystals is difficult to obtain from these sparsely distributed, small crystals on the basis of 2D images. Crystal size distributions obtained from both methods are otherwise similar. - Ce travail de recherche a été entrepris dans le but d'étudier les processus de fusion partielle dans les roches fortement métamorphiques de l'auréole de contact de Little Cottonwood (Utah, USA) et ceci afin de comprendre la génération de liquide de fusion, la migration de ces liquides et la géométrie de la distribution initiale des liquides de fusion à l'échelle du grain durant l'anatexie de la croûte. L'emplacement du petit massif intrusif de Little Cottonwood a produit une auréole de contact dans les roches pélitiques encaissantes appartenant à la Foimation du Big Cottonwood (BC). Les isogrades métamorphiques dans les roches pélitiques varient de l'isograde de la biotite à la deuxième isograde de la sillimanite en fonction de la distance par rapport au massif intrusif. Les migmatites sont restreintes aux zones montrant le plus haut degré métamorphique et résultent de la fusion partielle des roches de la Formation de BC. Le premier liquide de fusion a été produit par la réaction de déshydratation combinée de la muscovite et de la biotite dans le champ de stabilité du feldspath potassique Pt de la sillimanite. L'extraction du liquide de fusion des pélites forme des restites (magnétites + cordiérite + aluminosilicate ± biotite) entourées par des zones de quartzites enrichies en feldspath. Cette texture est le résultat de l'infiltration graduelle du liquide de fusion partielle dans les quartzites. Des accumulations distinctes et plus larges de liquide de fusion ont lieu dans des domaines d'extension ou de transpression tels que les boudins, les veines, et les zones de cisaillement ductile. La composition des liquides de fusion est similaire à celle des liquides pegmatoïdes, et ces liquides sont apparemment très mobiles et capables d'infiltrer les quartzites. Ces liquides de fusion ont la même composition que les premiers liquides produits dans les expériences hydrotheunales de fusion partielle à 2kbar et entre 700-800° C sur les roches finement grenues et hautement métamorphiques (andalousite-cordiérite-biotite zone) de la Formation de BC. Les liquides de fusion obtenus expérimentalement sont riches en eau et sont en déséquilibre avec la roche en fusion. La composition initiale des liquides de fusion est hétérogène pour les expériences de courte durée et reflète l'absence d'équilibre chimique entre les différentes zones d'accumulation des liquides de fusion. L'hétérogénéité à l'échelle du noyau s'estompe avec le temps et témoigne de l'homogénéisation de la composition des liquides de fusion. Par ailleurs, on observe parallèlement un décalage de la composition des liquides vers des compositions plus riches en silice au cours du temps. Le contenu en silice des liquides de fusion évolue vers un liquide pegmatitique en raison des réactions liquides/minéraux. Les textures des liquides de fusion indiquent que le transport des liquides est plus efficace le long des bordures de grains bordés par des grains différents. Aucun changement apparent du volume total n'est visible. L'hétérogénéité des liquides s'accompagne d'un gradient de potentiel chimique qui sert de moteur principal à la migration des liquides et à la distribution des liquides durant la fusion. Un sujet complémentaire de ce travail de thèse réside dans l'étude de la distribution de la taille des cristaux opaques dans les pélites finement grenues et fortement métamorphiques de la Formation de Big Cottonwood. Les distributions de taille ont été obtenues suite à l'analyse d'images 3D acquise par tomographie ainsi que par analyse de lames minces. La microtomographie par rayon X fournit une distribution de taille précise sur une marge restreinte (- un facteur de taille 20 dans une seule image 3D), alors que le nombre absolu de cristaux est difficile à obtenir sur la base d'image 2D en raison de la petite taille et de la faible abondance de ces cristaux. Les distributions de taille obtenues par les deux méthodes sont sinon similaire. Abstact: Chemical differentiation of the primitive Earth was due to melting and separation of melts. Today, melt generation and emplacement is still the dominant process for the growth of the crust. Most granite formation is due to partial melting of the lower crust, followed by transport of magma through the crust to the shallow crust where it is emplaced. Partial melting and melt segregation are essential steps before such a granitic magma can ascent through the crust. The chemistry and physics of partial melting and segregation is complex. Hence detailed studies, in which field observations yield critical information that can be compared to experimental observations, are crucial to the understanding of these fundamental processes that lead and are leading to the chemical stratification of the Earth. The research presented in this thesis is a combined field and experimental study of partial melting of high-grade meta-pelitic rocks of the Little Cottonwood contact aureole (Utah, USA). Contact metamorphic rocks are ideal for textural studies of melt generation, since the relatively short times of the metamorphic event prevents much of the recrystallization which plagues textural studies of lower crustal rocks. The purpose of the study is to characterize melt generation, identify melting reactions, and to constrain melt formation, segregation and migration mechanisms. In parallel an experimental study was undertaken to investigate melt in the high grade meta pelitic rocks, to confirm melt composition, and to compare textures of the partial molten rock cores in the absence of deformation. Results show that a pegmatoidal melt is produced by partial melting of the pelitic rocks. This melt is highly mobile. It is capable of pervasive infiltration of the adjacent quartzite. Infiltration results in rounded quartz grains bordered by a thin feldspar rim. Using computed micro X-ray tomography these melt networks can be imaged. The infiltrated melt leads to rheological weakening and to a decompaction of the solid quartzite. Such decompaction can explain the recent discovery of abundant xenocrysts in many magmas, since it favors the isolation of mineral grains. Pervasive infiltration is apparently strongly influenced by melt viscosity and melt-crystal wetting behavior, both of which depend on the water content of melt and the temperature. In all experiments the first melt is produced on grain boundaries, dominantly by the local minerals. Grain scale heterogeneity of a melting rock leads thus to chemical concentration gradients in the melt, which are the driving force for initial melt migration. Pervasive melt films along grain boundaries leading to an interconnected network are immediately established. The initial chemical heterogeneities in the melt diminish with time. Résumé large public: La différenciation chimique de la Terre primitive est la conséquence de la fusion des roches et de la séparation des liquides qui en résultent. Aujourd'hui, la production de liquide magmatique est toujours le mécanisme dominant pour la croissance de la croûte terrestre. Ainsi la formation de la plupart des granites est un processus qui implique la production de magma par fusion partielle de la croûte inférieure, la migration de ces magmas à travers la croûte et finalement son emplacement dans les niveaux superficielle de la croûte terrestre. Au cours de cette évolution, les processus de fusion partielle et de ségrégation sont des étapes indispensables à l'ascension des granites à travers la croûte. Les conditions physico-chimiques nécessaires à la fusion partielle et à l'extraction de ces liquides sont complexes. C'est pourquoi des études détaillées des processus de fusion partielle sont cruciales pour la compréhension de ces mécanismes fondamentaux responsables de la stratification chimique de la Terre. Parmi ces études, les observations de terrain apportent notamment des informations déterminantes qui peuvent être comparées aux données expérimentales. Le travail de recherche présenté dans ce mémoire de thèse associe études de terrain et données expérimentales sur la fusion partielle des roches pélitiques de haut degré métamorphiques provenant de l'auréole de contact de Little Cottonwood (Utah, USA). Les roches du métamorphisme de contact sont idéales pour l'étude de la folination de liquide de fusion. En effet, la durée relativement courte de ce type d'événement métamorphique prévient en grande partie la recristallisation qui perturbe les études de texture des roches dans la croûte inférieure. Le but de cette étude est de caractériser la génération des liquides de fusion, d'identifier les réactions responsables de la fusion de ces roches et de contraindre la formation de ces liquides et leur mécanisme de ségrégation et de migration. Parallèlement, des travaux expérimentaux ont été entrepris pour reproduire la fusion partielle de ces roches en laboratoire. Cette étude a été effectuée dans le but de confirmer la composition chimique des liquides, et de comparer les textures obtenues en l'absence de déformation. Les résultats montrent qu'un liquide de fusion pegmatoïde est produit par fusion partielle des roches pélitiques. La grande mobilité de ce liquide permet une infiltration pénétrative dans les quarzites. Ces infiltrations se manifestent par des grains de quartz arrondis entourés par une fine bordure de feldspath. L'utilisation de la tomography à rayons X a permis d'obtenir des images de ce réseau de liquide de fusion. L'infiltration de liquide de fusion entraîne un affaiblissement de la rhéologie de la roche ainsi qu'une décompaction des quartzites massifs. Une telle décompaction peut expliquer la découverte récente d'abondants xénocristaux dans beaucoup de magmas, puisque elle favorise l'isolation des minéraux. L'infiltration pénétrative est apparemment fortement influencée par la viscosité du fluide de fusion et le comportement de la tension superficielle entre les cristaux et le liquide, les deux étant dépendant du contenu en eau dans le liquide de fusion et de la température. Dans toutes les expériences, le premier liquide est produit sur les bordures de grains, principalement par les minéraux locaux. L'hétérogénéité à l'échelle des grains d'une roche en fusion conduit donc à un gradient de concentration chimique dans le liquide, qui sert de moteur à l'initiation de la migration du liquide. Des fines couches de liquide de fusion le long de bordures de grains formant un réseau enchevêtré s'établit immédiatement. Les hétérogénéités chimiques initiales dans le liquide s'estompent avec le temps.

Formation of aluminosilicate-bearing quartz veins in the Simano nappe (Central Alps): structural, thermobarometric and oxygen isotope constraints

We combined structural analysis, thermobarometry and oxygen isotope geochemistry to constrain the evolution of kyanite and/or andalusite-bearing quartz veins from the amphibolite facies metapelites of the Simano nappe, in the Central Alps of Switzerland. The Simano nappe records a complex polyphase tectonic evolution associated with nappe stacking during Tertiary Alpine collision (D1). The second regional deformation phase (132) is responsible for the main penetrative schistosity and mineral lineation, and formed during top-to-the-north thrusting. During the next stage of deformation (D3) the aluminosilicate-bearing veins formed by crystallization in tension gashes, in tectonic shadows of boudins, as well as along shear bands associated with top-to-the-north shearing. D2 and D3 are coeval with the Early Miocene metamorphic peak, characterised by kyanite + staurolite + garnet + biotite assemblages in metapelites. The peak pressure (P) and temperature (T) conditions recorded are constrained by multiple-equilibrium thermobarometry at 630 +/- 20 degrees C and 8.5 +/- 1 kbar (similar to 27 km depth), which is in agreement with oxygen isotope thermometry indicating isotopic equilibration of quartz-kyanite pairs at 670 +/- 50 degrees C. Quartz-kyanite pairs from the aluminosilicate-bearing quartz veins yield equilibration temperatures of 645 +/- 20 degrees C, confirming that the veins formed under conditions near metamorphic peak. Quartz and kyanite from veins and the surrounding metapelites have comparable isotopic compositions. Local intergranular diffusion in the border of the veins controls the mass-transfer and the growth of the product assemblage, inducing local mobilization of SiO2 and Al2O3. Andalusite is absent from the host rocks, but it is common in quartz veins, where it often pseudomorphs kyanite. For andalusite to be stable at T-max, the pressure in the veins must have been substantially lower than lithostatic. An alternative explanation consistent with structural observations would be inheritance by andalusite of the kyanite isotopic signature during polymorphic transformation after the metamorphic peak.

The Mont-Mort metapelites: Variscan metamorphism and geodynamic context (Brianconnais basement, Western Alps, Switzerland)

The Mont-Mort metapelites are one of the best preserved relies of the Variscan unit in the Brianconnais basement. These micaschists crystallized during a poly-phase metamorphic cycle, under amphibolite facies conditions. Mineral parageneses and geothermobarometric calculations indicate a two-stage evolution. Stage (1) (550-600 degrees C and 5-8 kbar) is documented by assemblages of zoned garnet, staurolite, kyanite(?), biotite, muscovite, quartz and pla gioclase. Stage (2) (550-600 degrees C and 2 kbar) is illustrated by assemblages of andalusite, sillimanite, muscovite, biotite. This metamorphic evolution is characterized by a nearly isothermal decompression path, terminating with the formation of andalusite-bearing veins. U-Pb monazite dates at 330 Ma and Ar-40/Ar-39 muscovite dates at 290-310 Ma (without substantial evidence of argon resetting) point to Variscan metamorphism and yield an estimate of the time interval between the thermal peak and the retrogression stage within this part of the Brianconnais basement. Restoring the Brianconnais and other Alpine basement units within an existing geodynamic model of Cordillera construction and destruction, it is possible to understand better the transition from a medium pressure/high temperature regime (collision with a peak metamorphism around 330 Ma) to low-P/high-T conditions (decompression in an extensional regime) with high geothermal gradient, as recorded by the successive Variscan parageneses within the Mont-Mort metapelites.

Physical volcanology, sedimentology, stratigraphy and petrochemistry of the Berry Creek metavolcanics: an Archean calc-alkaline complex, Lake of the Woods, Ontario

The steeply dipping, isoclinally folded early Precambrian (Archean) Berry Creek Metavolcanic Complex comprises primary to resedimented pyroclastic, epiclastic and autoclastic deposits. Tephra erupted from central volcanic edifices was dumped by mass flow mechanisms into peripheral volcanosedimentary depressions. Sedimentation has been essentially contemporaneous with eruption and transport of tephra. The monolithic to heterolithic tuffaceous horizons are interpreted as subaerial to subaqueous pumice and ash flows, secondary debris flows, lahars, slump deposits and turbidites. Monolithic debris flows, derived from crumble breccia and dcme talus, formed during downslope collapse and subsequent gravity flowage. Heterolithic tuff, lahars and lava flow morphologies suggest at least temporary emergence of the edifice. Local collapse may have accompanied pyroclastic volcanism. The tephra, produced by hydromagmatic to magmatic eruptions, were rapidly transported, by primary and secondary mechanisms, to a shallow littoral to deep water subaqueous fan developed upon the subjacent mafic metavolcanic platform. Deposition resulted from traction, traction carpet, and suspension sedimentation from laminar to turbulent flows. Facies mapping revealed proximal (channel to overbank) to distal facies epiclastics (greywackes, argillite) intercalated with proximal vent to medial fan facies crystal rich ash flows, debris flows, bedded tuff and shallow water to deep water lava flows. Framework and matrix support debris flows exhibit a variety of subaqueous sedimentary structures, e.g., coarse tail grading, double grading, inverse to normal grading, graded stratified pebbly horizons, erosional channels. Pelitic to psammitic AE turbidites also contain primary stru~tures, e.g., flames, load casts, dewatering pipes. Despite low to intermediate pressure greenschist to amphibolite grade metamorphism and variably penetrative deformation, relicts of pumice fragments and shards were recognized as recrystallized quartzofeldspathic pseudomorphs. The mafic to felsic metavolcanics and metasediments contain blasts of hornblende, actinolite, garnet, pistacitic epidote, staurolite, albitic plagioclase, and rarely andalusite and cordierite. The mafic metavolcanics (Adams River Bay, Black River, Kenu Lake, Lobstick Bay, Snake Bay) display _holeiitic trends with komatiitic affinities. Chemical variations are consistent with high level fractionation of olivine, plagioclase, amphibole, and later magnetite from a parental komatiite. The intermediate to felsic (64-74% Si02) metavolcanics generally exhibit calc-alkaline trends. The compositional discontinuity, defined by major and trace element diversity, can be explained by a mechanism involving two different magma sources. Application of fractionation series models are inconsistent with the observed data. The tholeiitic basalts and basaltic andesites are probably derived by low pressure fractionation of a depleted (high degree of partial melting) mantle source. The depleted (low Y, Zr) calc-alkaline metavolcanics may be produced by partial melting of a geochemically evolved source, e.g., tonalitetrondhjemite, garnet amphibolite or hydrous basalt.

Caracterização de minerais pesados ao longo do Rio Piranhas-Açu/RN distribuição e proveniência

This dissertation deals with the characterization, distribution and provenience of heavy minerals along the Piranhas-Açu River, from the City of Parelhas (Seridó River) to your mouth at the City of Macau-RN. Many heavy minerals species were recorded in this study: clinoamphibole, epidote (including zoisite), garnet, sillimanite, tourmaline, staurolite, andalusite, zircon, rutile, augite, ilmenite, hematite and magnetite. Major transparent minerals, those forming more than 5% of some assemblages, are hornblende, epidote, tourmaline, staurolite and zircon. Predominant opaque mineral is ilmenite. Six assemblages were identified along the river: (i) Garnet-hornblende-tourmaline with sillimanite, when cutting rocks of the Seridó Formation; (ii) Hornblende-garnet-zircon, when crossing rocks of the Caicó gnaisse-migmatitic Complex; (iii) Hornblende-zircon-epidote-staurolite, when draining rocks of the Jucurutu Formation; (iv) Hornblende-zircon-epidote, when cutting rocks of the Açu Formation; (v) Hornblende-zircon-staurolite, on the lowermost Açu River, when crossing limestones of the Jandaíra Formation and (vi) Zircon-tourmaline-staurolite in the Açu River mouth (Cenozoic rocks) where coastal process dominate. Mineral ratios that reflect differences in grain shape, density, and selective chemical decomposition were used in an attempt to isolate the effects of source and process as controls of mineral variability. Reworking of the sediments was regionally effective in selective sorting; the more equant minerals (e.g. epidote) and heavier minerals (e.g. opaques) had a higher probability of being selected for permanent deposition during reworking. The processes of selective decomposition stand out at the river mouth. A priori knowledge of provenance, associated with the assemblage distribution and effects of process were utilized to the interpretations, that points to the follow provenances: hornblende comes from micashists of the Seridó Formation, orthognaisses and amphibolites of the Caico Complex, paragnaisses and paranphibolites of the Jucurutu Formation and granites intrusions; epidote comes from paragnaisses and calciosilicatics of the Jucurutu Formation, granites intrusions (-Npy3al/ca and -Npy3mz, gravels deposits and Açu Formation; Andalusite and staurolite come from the Seridó Formation; Sillimanite, tourmaline and garnet come from micashists of the Seridó Formation, as well as from quartzites of the Equador Formation; Zircon comes from Precambrian rocks (pink and prismatic zircon) and from sediments of several cycles (round zircon); Opaques come from all rocks cutted for the Piranhas-Açu River; Rutile comes from metamorphic rocks, in general; Augite comes from the Ceará-Mirim, Serra do Cuó and Macau volcanisms. The texture of gravels deposits reveals a sediment transport mechanisms by traction-current processes, together with a diagenetic clay matrix suggests a hot-humid environments for deposition. The presence of unstable heavy minerals assemblages, as well as pebbles of different composition and degrees of rounding and esfericity, indicate more than one source. The occurrence of calcio/alkaline granites suites, in areas closed to the gravel deposits, suggests that these intrusions are the main source of sediments. This could explain for instance, the significant amounts of epidote and presence of unstable heavy minerals (e.g. hornblende). The analyses of heavy minerals also show significante variability between the modern (Piranhas-Açu) and ancestral (Açu Formation) river sediments. In general, these variations reflect relatively higher unstable and lower stable heavy minerals contents of the modern Piranhas-Açu sediments. The absence of significant compositional differences probably reflects uniform weathering conditions

Petrologia do magmatismo tardi-brasiliano no Maciço São José de Campestre(RN/PB), com ênfase no Plúton Alcalino Caxexa

The area studied is located on the north-easternmost portion of the Borborema Province, on the so-called São José de Campestre Massif, States of RN and PB, Northeast Brazil. Field relations and petrographic, geochemical and isotope data permitted the separation of five suites of plutonic rocks: alkali-feldspar granite (Caxexa Pluton), which constitutes the main subject of this dissertation, amphibole-biotite granite (Cabeçudo Pluton), biotite microgranite, gabbronorite to monzonite (Basic to Intermediate Suite) and aluminous granitoid. The Caxexa Pluton is laterally associated to the Remígio Pocinhos Shear Zone, with its emplacement along the mylonitic contact between the gneissic basement and the micashists. This pluton corresponds to a syntectonic intrusion elongated in the N-S direction, with about 50 km2 of outcropping surface. It is composed exclusively of alkali-feldspar granites, having clinopyroxene (aegirine-augite and hedenbergite), andradite-rich garnet, sphene and magnetite. It is classified geochemically as high silica rocks (>70 % wt), metaluminous to slightly peraluminous (normative corindon < 1%), with high total alkalis (>10% wt), Sr, iron number (#Fe=90-98) and agpaitic index (0.86-1.00), and positive europium anomaly. The Cabeçudo Pluton is composed of porphyritic rocks, commonly containing basic to intermediate magmatic enclaves often with mingling and mixing textures. Petrographically, it presents k-feldspar and plagioclase phenocrysts as the essential minerals, besides the accessories amphibole, biotite, sphene and magnetite. It is metaluminous and shows characteristics transitional between the calc-alkaline and alkaline series (or monzonitic subalkaline). Its REE content is greater than those ones of the Caxexa Pluton and biotite microgranite, and all spectra have negative europium anomalies. The biotite microgranites occur mainly on the central and eastern portion of the mapped area, as dykes and sheets with decimetric thickness, hosted principally in orthogneisses and micashists. Their field relationships as regards the Caxexa and Cabeçudo plutons suggested that they are late-tectonic intrusions. They are typically biotite granites, having also sphene, amphibole, allanite, opaques and zircon in the accessory assemblage. Geochemically they can be distinguished from the porphyritic types because the biotite microgranites are more evolved, peraluminous, and have more fractionated REE spectra. The Basic to Intermediate rocks form a volumetrically expressive elliptical, kilometric scale body on the Southeast, as well as sheets in micashists. They are classified as gabbronorites to monzonites, with the two pyroxenes and biotite, besides subordinated amounts of amphibole, sphene, ilmenite and allanite. These rocks do not show a well-defined geochemical trend, however they may possibly represent a monzonitic (shoshonitic) series. Their REE spectra have negative europium anomalies and REE contents greater than the other suites. The aluminous granitoids are volumetrically restricted, and have been observed in close association with migmatised micashists bordering the gabbronorite pluton. They are composed of almandine-rich garnet, andalusite, biotite and muscovite, and are akin to the peraluminous suites. Rb-Sr (whole rock) and Sm-Nd (whole-rock and mineral) isotopes furnished a minimum estimate of the crystallization (578±14 Ma) and the final resetting age of the Rb-Sr system (536±4 Ma) in the Caxexa Pluton. The aluminous granitoid has a Sm-Nd garnet age similar to that one of the Caxexa Pluton, that is 574±67 Ma. The strong interaction of shear bands and pegmatite dykes favoured the opening of the Rb-Sr system for the Caxexa Pluton and biotite microgranite. The amphibole-plagioclase geothermometer and the Al-in amphibole geobarometer indicate minimum conditions of 560°C and 7 kbar for the Cabeçudo Pluton, 730°C and 6 kbar for the microgranite and 743°C and 5 kbar for the basic to intermediate suite. The Zr saturation geothermometer reveals temperatures of respectively 855°C, 812°C and 957°C for those suites, whereas the Caxexa Pluton shows temperatures of around 757°C. The Caxexa, Cabeçudo and microgranites suites crystallized under high fO2 (presence of magnetite). On the other hand, the occurrence of ilmenite suggests less oxidant conditions in the basic to intermediate suite. Field relations demonstrate the intrusive character of the granitoids into a tectonically relatively stable continental crust. This is corroborated by petrographic and geochemical data, which suggest a late- or post-collisional tectonic context. It follows that the generation and emplacement of those granitoid suites is related to the latest events of the Brasiliano orogeny. Finally, the relationships between eNd (600 Ma), TDM (Nd) and initial Sr isotope ratio (ISr) do not permit to define the precise sources of the granitoids. Nevertheless, trace element modelling and isotopic comparisons suggest the participation of the metasomatised mantle in the generation of these suites, probably modified by different degrees of crustal contamination. In this way, a metasomatised mantle would not be a particular characteristic of the Neoproterozoic lithosphere, but a remarkable feature of this portion of the Borborema Province since Archaean and Paleoproterozoic times.

Proveniência de arenitos albianos (Grupo Itapecuru), borda leste da bacia de São Luís-Grajaú, Maranhão, usando análise de minerais pesados e química mineral

Depósitos albianos da bacia de São Luís-Grajaú, antigamente conhecidos apenas em subsuperfície como ‘Unidade Indiferenciada’ do Grupo Itapecuru, foram recentemente encontrados ao longo do rio Itapecuru, na parte leste desta bacia. São argilitos avermelhados, esverdeados a cinzas, arenitos estratificados e maciços e subordinadamente calcários, interpretados como depósitos de delta progradante para ENE/E e ESE e conectado a uma plataforma restrita. Para determinar a proveniência de arenitos albianos, foram coletadas 18 amostras para estudos de minerais pesados (fração 0,062-0,125 mm) usando-se microscópio petrográfico convencional e microscópio eletrônico de varredura. Os arenitos foram classificados como quartzo-arenito moderadamente a bem selecionado, cimentado por dolomita, cujos principais minerais pesados são zircão (4-70%), granada (12-74%), turmalina (3-20%), estaurolita (1-9%), rutilo (1-8%) e barita (0-55%), enquanto cianita, anatásio (autigênico), anfibólio (hornblenda), andaluzita, sillimanita, espinélio e ilmenita ocorrem raramente. A maioria dos grãos é irregular angulosa, mas grãos bem arredondados, particularmente de turmalina e zircão, também estão presentes. Texturas superficiais incluem fraturas conchoidais, marcas de percussão em V e pequenos buracos, estes últimos em grãos arredondados de turmalina e zircão, enquanto feições de corrosão estão principalmente presentes em barita (cavidades rômbicas), cianita, estaurolita (superfície mamilar) e granada (facetas bem formadas por dissolução). Grãos de zircão, com texturas de zoneamento oscilatório e razões U/Th ≥ 0,5 e Zr/Hf média de 29, indicam proveniência de granitos e migmatitos, enquanto os tipos de turmalina, determinados como dravita e shorlita, são oriundos, principalmente, de metapelitos e metapsamitos aluminosos e/ou pobres em Al, com menor contribuição de granitos e rochas meta-ultramáficas. As granadas, por sua vez, são ricas em almandina e têm baixos teores dos componentes de espessartita, grossulária e piropo. Suas fontes potenciais são rochas metamórficas de baixo a médio grau e granitos. Com base em análises de minerais pesados e progradação do sistema deltaico para ENE/E e ESE, as áreas mais prováveis como fontes potenciais de arenitos albianos são o cráton São Luís, os cinturões neoproterozóicos Araguaia e Gurupi, bem como a bacia paleozóica do Parnaíba, esta fornecendo sedimentos de grãos arredondados.

Geologia, mineralogia e geoquímica dos fosfatos de Sapucaia (Bonito - PA)

O depósito mineral de Sapucaia, situado no município de Bonito, região nordeste do Estado do Pará, é parte de um conjunto de ocorrências de fosfatos de alumínio lateríticos localizados predominantemente ao longo da zona costeira dos estados do Pará e Maranhão. Estes depósitos foram alvos de estudo desde o início do século passado, quando as primeiras descrições de “bauxitas fosforosas” foram mencionadas na região NW do Maranhão. Nas últimas décadas, com o crescimento acentuado da demanda por produtos fertilizantes pelo mercado agrícola mundial, diversos projetos de exploração mineral foram iniciados ou tiveram seus recursos ampliados no território brasileiro, dentre estes destaca-se a viabilização econômica de depósitos de fosfatos aluminosos, como o de Sapucaia, que vem a ser o primeiro projeto econômico mineral de produção e comercialização de termofosfatos do Brasil. Este trabalho teve como principal objetivo caracterizar a geologia, a constituição mineralógica e a geoquímica do perfil laterítico alumino-fosfático do morro Sapucaia. A macrorregião abrange terrenos dominados em sua maioria por rochas pré-cambrianas a paleozóicas, localmente definidas pela Formação Pirabas, Formação Barreiras, Latossolos e sedimentos recentes. A morfologia do depósito é caracterizada por um discreto morrote alongado que apresenta suaves e contínuos declives em suas bordas, e que tornam raras as exposições naturais dos horizontes do perfil laterítico. Desta forma, a metodologia aplicada para a caracterização do depósito tomou como base o programa de pesquisa geológica executada pela Fosfatar Mineração, até então detentora dos respectivos direitos minerais, onde foram disponibilizadas duas trincheiras e amostras de 8 testemunhos de sondagem. A amostragem limitou-se à extensão litológica do perfil laterítico, com a seleção de 44 amostras em intervalos médios de 1m, e que foram submetidas a uma rota de preparação e análise em laboratório. Em consonância com as demais ocorrências da região do Gurupi, os fosfatos de Sapucaia constituem um horizonte individualizado, de geometria predominantemente tabular, denominado simplesmente de horizonte de fosfatos de alumínio ou crosta aluminofosfática, que varia texturalmente de maciça a cavernosa, porosa a microporosa, que para o topo grada para uma crosta ferroalumino fosfática, tipo pele-de-onça, compacta a cavernosa, composta por nódulos de hematita e/ou goethita cimentados por fosfatos de alumínio, com características similares aos do horizonte de fosfatos subjacente. A crosta aluminofosfática, para a base do perfil, grada para um espesso horizonte argiloso caulinítico com níveis arenosos, que repousa sobre sedimentos heterolíticos intemperizados de granulação fina, aspecto argiloso, por vezes sericítico, intercalados por horizontes arenosos, e que não possuem correlação aparente com as demais rochas aflorantes da geologia na região. Aproximadamente 40% da superfície do morro é encoberta por colúvio composto por fragmentos mineralizados da crosta e por sedimentos arenosos da Formação Barreiras. Na crosta, os fosfatos de alumínio estão representados predominantemente pelo subgrupo da crandallita: i) série crandallita-goyazita (média de 57,3%); ii) woodhouseíta-svanbergita (média de 15,8%); e pela iii) wardita-millisita (média de 5,1%). Associados aos fosfatos encontram-se hematita, goethita, quartzo, caulinita, muscovita e anatásio, com volumes que variam segundo o horizonte laterítico correspondente. Como os minerais pesados em nível acessório a raro estão zircão, estaurolita, turmalina, anatásio, andalusita e silimanita. O horizonte de fosfatos, bem como a crosta ferroalumínio-fosfática, mostra-se claramente rica em P₂O₅, além de Fe₂O₃, CaO, Na₂O, SrO, SO₃, Th, Ta e em terras-raras leves como La e Ce em relação ao horizonte saprolítico. Os teores de SiO₂ são consideravelmente elevados, porém muito inferiores aqueles identificados no horizonte argiloso sotoposto. No perfil como um todo, observa-se uma correlação inversa entre SiO₂ e Al₂O₃; entre Al₂O₃ e Fe₂O₃, e positiva entre SiO₂ e Fe₂O₃, que ratificam a natureza laterítica do perfil. Diferente do que é esperado para lateritos bauxíticos, os teores de P₂O₅, CaO, Na₂O, SrO e SO₃ são fortemente elevados, concentrações consideradas típicas de depósitos de fosfatos de alumínio ricos em crandallita-goyazita e woodhouseítasvanbergita. A sucessão dos horizontes, sua composição mineralógica, e os padrões geoquímicos permitem correlacionar o presente depósito com os demais fosfatos de alumínio da região, mais especificamente Jandiá (Pará) e Trauíra (Maranhão), bem como outros situados além do território brasileiro, indicando portanto, que os fosfatos de alumínio de Sapucaia são produtos da gênese de um perfil laterítico maturo e completo, cuja rocha fonte pode estar relacionada a rochas mineralizadas em fósforo, tais como as observadas na Formação Pimenteiras, parcialmente aflorante na borda da Bacia do Parnaíba. Possivelmente, o atual corpo de minério integrou a paleocosta do mar de Pirabas, uma vez que furos de sondagem às proximidades do corpo deixaram claro a relação de contato lateral entre estas unidades.

Geochemical constraints on blueschist- and amphibolite-facies rocks of the Central Cordillera of Colombia: the Andean Barragan region

Subduction zones are one of the most characteristic features of planet Earth. Convergent plate junctions exert enormous influence on the formation and recycling of continental crust, and they are also responsible for major mineral resources and earthquakes, which are of crucial importance for society. A subduction-related geologic unit containing high-pressure rocks occurs in the Barragan area (Valle del Cauca Department) on the western flank of the Central Cordillera of the Colombian Andes. Blueschists and amphibolites, serpentinized meta-ultramafic rocks, graphite-chlorite-muscovite-quartz schists, protocataclasites, and graphite-chlorite-andalusite-andesine-garnet-muscovite +/- titanite schists are exposed in this region. In spite of the petrotectonic importance of blueschists, the high-pressure metamorphism of the Central Cordillera of Colombia has been rarely studied. New geochemical data indicate that protoliths of the blueschist- and amphibolite-facies rocks possessed normal mid-ocean ridge basalt bulk compositions. Ar-40/Ar-39 geochronology for a metapelite rock associated with the blueschists shows a plateau age of similar to 120 million years. We suggest that high-P/T conditions were present from similar to 150 to 125 Ma, depending on the model of generation and exhumation considered.

Metamorfismo ercinico di bassa-pressione: evoluzione tettonico-metamorfica del complesso di mandatoriccio (massiccio della Sila - Calabria)

Low-pressure/high-temperature (LP/HT) metamorphic belts are characterised by rocks that experienced abnormal heat flow in shallow crustal levels (T > 600 °C; P < 4 kbar) resulting in anomalous geothermal gradients (60-150 °C/km). The abnormal amount of heat has been related to crustal underplating of mantle-derived basic magmas or to thermal perturbation linked to intrusion of large volumes of granitoids in the intermediate crust. In particular, in this latter context, magmatic or aqueous fluids are able to transport relevant amounts of heat by advection, thus favouring regional LP/HT metamorphism. However, the thermal perturbation consequent to heat released by cooling magmas is responsible also for contact metamorphic effects. A first problem is that time and space relationships between regional LP/HT metamorphism and contact metamorphism are usually unclear. A second problem is related to the high temperature conditions reached at different crustal levels. These, in some cases, can completely erase the previous metamorphic history. Notwithstanding this problem is very marked in lower crustal levels, petrologic and geochronologic studies usually concentrate in these attractive portions of the crust. However, only in the intermediate/upper-crustal levels of a LP/HT metamorphic belt the tectono-metamorphic events preceding the temperature peak, usually not preserved in the lower crustal portions, can be readily unravelled. The Hercynian Orogen of Western Europe is a well-documented example of a continental collision zone with widespread LP/HT metamorphism, intense crustal anatexis and granite magmatism. Owing to the exposure of a nearly continuous cross-section of the Hercynian continental crust, the Sila massif (northern Calabria) represents a favourable area to understand large-scale relationships between granitoids and LP/HT metamorphic rocks, and to discriminate regional LP/HT metamorphic events from contact metamorphic effects. Granulite-facies rocks of the lower crust and greenschist- to amphibolite-facies rocks of the intermediate-upper crust are separated by granitoids emplaced into the intermediate level during the late stages of the Hercynian orogeny. Up to now, advanced petrologic studies have been focused mostly in understanding P-T evolution of deeper crustal levels and magmatic bodies, whereas the metamorphic history of the shallower crustal levels is poorly constrained. The Hercynian upper crust exposed in Sila has been subdivided in two different metamorphic complexes by previous authors: the low- to very low-grade Bocchigliero complex and the greenschist- to amphibolite-facies Mandatoriccio complex. The latter contains favourable mineral assemblages in order to unravel the tectono-metamorphic evolution of the Hercynian upper crust. The Mandatoriccio complex consists mainly of metapelites, meta-arenites, acid metavolcanites and metabasites with rare intercalations of marbles and orthogneisses. Siliciclastic metasediments show a static porphyroblastic growth mainly of biotite, garnet, andalusite, staurolite and muscovite, whereas cordierite and fibrolite are less common. U-Pb ages and internal features of zircons suggest that the protoliths of the Mandatoriccio complex formed in a sedimentary basin filled by Cambrian to Silurian magmatic products as well as by siliciclastic sediments derived from older igneous and metamorphic rocks. In some localities, metamorphic rocks are injected by numerous aplite/pegmatite veins. Small granite bodies are also present and are always associated to spotted schists with large porphyroblasts. They occur along a NW-SE trending transcurrent cataclastic fault zone, which represents the tectonic contact between the Bocchigliero and the Mandatoriccio complexes. This cataclastic fault zone shows evidence of activity at least from middle-Miocene to Recent, indicating that brittle deformation post-dated the Hercynian orogeny. P-T pseudosections show that micaschists and paragneisses of the Mandatoriccio complex followed a clockwise P-T path characterised by four main prograde phases: thickening, peak-pressure condition, decompression and peak-temperature condition. During the thickening phase, garnet blastesis started up with spessartine-rich syntectonic core developed within micaschists and paragneisses. Coevally (340 ± 9.6 Ma), mafic sills and dykes injected the upper crustal volcaniclastic sedimentary sequence of the Mandatoriccio complex. After reaching the peak-pressure condition (≈4 kbar), the upper crust experienced a period of deformation quiescence marked by the static overgrowths of S2 by Almandine-rich-garnet rims and by porphyroblasts of biotite and staurolite. Probably, this metamorphic phase is related to isotherms relaxation after the thickening episode recorder by the Rb/Sr isotopic system (326 ± 6 Ma isochron age). The post-collisional period was mainly characterised by decompression with increasing temperature. This stage is documented by the andalusite+biotite coronas overgrown on staurolite porphyroblasts and represents a critical point of the metamorphic history, since metamorphic rocks begin to record a significant thermal perturbation. Peak-temperature conditions (≈620 °C) were reached at the end of this stage. They are well constrained by some reaction textures and mineral assemblages observed almost exclusively within paragneisses. The later appearance of fibrolitic sillimanite documents a small excursion of the P-T path across the And-Sil boundary due to the heating. Stephanian U-Pb ages of monazite crystals from the paragneiss, can be related to this heating phase. Similar monazite U-Pb ages from the micaschist combined with the lack of fibrolitic sillimanite suggest that, during the same thermal perturbation, micaschists recorded temperatures slightly lower than those reached by paragneisses. The metamorphic history ended with the crystallisation of cordierite mainly at the expense of andalusite. Consequently, the Ms+Bt+St+And+Sill+Crd mineral assemblage observed in the paragneisses is the result of a polyphasic evolution and is characterised by the metastable persistence of the staurolite in the stability fields of the cordierite. Geologic, geochronologic and petrographic data suggest that the thermal peak recorded by the intermediate/upper crust could be strictly connected with the emplacement of large amounts of granitoid magmas in the middle crust. Probably, the lithospheric extension in the relatively heated crust favoured ascent and emplacement of granitoids and further exhumation of metamorphic rocks. After a comparison among the tectono-metamorphic evolutions of the different Hercynian crustal levels exposed in Sila, it is concluded that the intermediate/upper crustal level offers the possibility to reconstruct a more detailed tectono-metamorphic history. The P-T paths proposed for the lower crustal levels probably underestimate the amount of the decompression. Apart from these considerations, the comparative analysis indicates that P-T paths at various crustal levels in the Sila cross section are well compatible with a unique geologic scenario, characterized by post-collisional extensional tectonics and magmas ascent.

The Christensen Sillimanite Deposit Southeast of Dillon, Montana

The minerals sillimanite, kyanite, andalusite, dumortierite, and topaz comprise a group of minerals whose high alumina content and physical properties are particularly desirable in the manufacture of refractory products. Sillimanite is the least plentiful of the minerals of this group, and for this reason it is not used extensively at the present time. However, it would be very desirable to the refractory industry if a suitable domestic source of supply could be established.