Paleomagnetic study of the Messejana Plasencia dyke (Portugal and Spain): A lower Jurassic paleopole for the Iberian plate

The only Iberian lower Jurassic palcomagnetic pole come from the "Central Atlantic Magmatic Province"-related Messejana Plasencia dyke, but the age and origin of its remanence have been a matter of discussion. With the aim of solving this uncertainty, and to go further into a better understanding of its emplacement and other possible tectonic features, a systematic paleomagnetic investigation of 40 sites (625 specimens) distributed all along the 530 kin of the Messejana Plasencia dyke has been carried out. Rock magnetic experiments indicate PSD low Ti-titanomagnetite and magnetite as the minerals carrying the NRM. The samples were mostly thermally demagnetized. Most sites exhibit a characteristic remanent component of normal polarity with the exception of two sites, where samples with reversed polarities have been observed. The paleomagnetic pole derived from a total of 35 valid sites is representative of the whole structure of the dyke, and statistically well defined, with values of PLa = 70.4 degrees N, PLo = 237.6 degrees E, K= 47.9 and A(95) = 3.5 degrees. Paleomagnetic data indicates that: (i) there is no evidence of a Cretaceous remagnetization in the dyke, as it was suggested; (ii) most of the dyke had a brief emplacement time; furthermore, two dyke intrusion events separated in time from it by at least 10,000 y have been detected; (iii) the high grouping of the VGPs directions suggests no important tectonic perturbations of the whole structure of the dyke since its intrusion time; (iv) the pole derived from this study is a good quality lower Jurassic paleopole for the Iberian plate; and (v) the Messejana Plasencia dyke paleopole for the Iberian plate is also in agreement with quality-selected European and North American lower Jurassic paleopoles and the magnetic anomalies data sets that are available for rotate them to Iberia.

Electrochemical and analytical investigation of passive films formed on stainless steels in alkaline media

Passive films were grown in potentiodynamic mode, by cyclic voltammetry on AISI 316 and AISI 304 stainless steels. The composition of these films was investigated by X-ray photoelectron spectroscopy (XPS). The electrochemical behaviour and the chemical composition of the passive films formed by cyclic voltammetry were compared to those of films grown under natural conditions (by immersion at open circuit potential, OCP) in alkaline solutions simulating concrete. The study included the effect of pH of the electrolyte and the effect of the presence of chloride ions. The XPS results revealed important changes in the passive film composition, which becomes enriched in chromium and depleted in magnetite as the pH decreases. On the other hand, the presence of chlorides promotes a more oxidised passive layer. The XPS results also showed relevant differences on the composition of the oxide layers for the films formed under cyclic voltammetry and/or under OCP.

The detrital origin of the Moncorvo ordovician ironstones

The Moncorvo Ordovician ironstones in northeastern Portugal consist of iron ore sedimentary horizons frequently interbanded with psamites and quartzites. Ore reserves may probably exceed 1 000 million tonnes and this makes Moncorvo the largest iron ore deposit in the European Union. Compact poorly banded massive layers may exceed 90 meters in thickness which is quite an extraordinary feature for a Phanerozoic deposit. If the thickness of Precambrian deposits may reach a few hundred meters, the thickness of Phanerozoic deposits never exceed a maximum of 15 meters generally forming a number of comparatively thin layers confined to a particular member of a sedimentary sequence. A detailed microscopic analysis of the ores revealed that initially a compact magnetite/quartzite layer, detrital in character (the magnetite occasionally showing chromite cores), was deposited by entrapment in near shore lagoons where rivers debouched, rather than in the open sea. This stage was followed by oscilating and transgressive shore lines which gave rise to breaks in sedimentation in combined river delta and shallow water marine environment where detrital material and fine iron oxide and clay suspensions were deposited in fluctuating environments. These events gave rise to layers of both magnetite (martite) and specularite intergrown with quartz, silicates and phosphates. Textural and mineralogical studies show that the deposits consist of ferruginous clastic sediments and are not chemically deposited cherts. Field, geological and palaeontological evidence also supports a detrital origin, the facies being typical of zones rich in oxygen and close to the feeding continent. The uncommon huge development of Moncorvo was due to the fact that the deposits occur in restricted basins on a continental platform were clastic sediments were predominantly deposited. Not only morphologically but also chemically the deposits are more similar to Precambrian iron formations than to Phanerozoic ironstones.

In vitro studies of gum arabic-coated magnetic nanoparticles with mammalian cell cultures

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Biotecnologia

Estudo do efeito do tratamento por laser de objectos arqueológicos ferrosos

Dissertação de Mestrado em Conservação e Restauro - Metais

Desenvolvimento de nanopartículas magnéticas para tratamento de cancro: estudo da síntese e estabilização das soluções coloidais de Fe3O4

Dissertação para obtenção do Grau de Mestre em Engenharia Biomédica

Chondrogenic differentiation within magnetic-responsive multilayered liquified capsules containing collagen II/TFG-β3 coated microparticles

The use of stem cells is a promising therapeutic approach for the substantial challenge to regenerate cartilage. Considering the two prerequisites, namely the use of a 3D system to enable the chondrogenic differentiation and growth factors to avoid dedifferentiation, the diffusion efficiency of essential biomolecules is an intrinsic issue. We already proposed a liquified bioencapsulation system containing solid microparticles as cell adhesion sites1. Here, we intend to use the optimized system towards chondrogenic differentiation by encapsulating stem cells and collagenII-TGF-β3 PLLA microparticles. As a proof-of-concept, magnetite-nanoparticles were incorporated into the multilayered membrane. This can be a great advantage after implantation procedures to fixate the capsules in situ with the held of an external magnetic patch and for the follow-up through imaging. Results showed that the production of glycosaminoglycans and the expression of cartilage-relevant markers (collagen II, Sox9, aggrecan, and COMP) increased up to 28 days, while hypertrophic (collagen X) and fibrotic (collagen I) markers were downregulated. The presence of nanofibers in the newly deposited ECM was visualized by SEM, which resembles the collagen fibrils of native cartilage. The presence of the major constituent of cartilage, collagen II, was detected by immunocytochemistry and afranin-O and alcian blue stainings revealed a basophilic ECM deposition, which is characteristic of neocartilage. These findings suggest that the proposed system may provide a suitable environment for chondrogenic differentiation.

A systematic study of the structural and magnetic properties of Mn-, Co-, and Ni-Doped Colloidal Fe3O4 nanoparticles

A series of colloidal MxFe3-xO4 (M = Mn, Co, Ni; x = 0–1) nanoparticles with diameters ranging from 6.8 to 11.6 nm was synthesized by hydrothermal reaction in aqueous medium at low temperature (200 °C). Energy-dispersive X-ray microa-nalysis and inductively coupled plasma spectrometry confirms that the actual elemental compositions agree well with the nominal ones. The structural properties of obtained nanoparticles were investigated by using powder X-ray diffraction, Raman scattering, Mössbauer spectroscopy, and electron microscopy. The results demonstrate that our synthesis technique leads to the formation of chemically uniform single-phase solid solution nanoparticles with cubic spinel structure, confirming the intrinsic doping. Magnetic studies showed that, in comparison to Fe3O4, the saturation magnetization of MxFe3-xO4 (M = Mn, Ni) decreases with increasing dopant concentration, while Co-doped samples showed similar saturation magnetizations. On other hand, whereas Mn- and Ni-doped nanoparticles exhibits superparamagnetic behavior at room temperature, ferromagnetism emerges for CoxFe3-xO4 nanoparticles, which can be tuned by the level of Co doping.

Oxygen isotope thermometry in carbonatites, Fuerteventura, Canary Islands, Spain

Crystallization temperatures of the oceanic carbonatites of Fuerteventura, Canary Islands, have been determined from oxygen isotope fractionations between calcite, silicate minerals (feldspar, pyroxene, biotite, and zircon) and magnetite. The measured fractionations have been interpreted in the light of late stage interactions with meteoric and/or magmatic water. Cathodoluminescence characteristics were investigated for the carbonatite minerals in order to determine the extent of alteration and to select unaltered samples. Oxygen isotope fractionations of minerals of unaltered samples yield crystallization temperatures between 450 and 960degreesC (average 710degreesC). The highest temperature is obtained from pyroxene-calcite pairs. The above range is in agreement with other carbonatite thermometric Studies. This is the first study that provides oxygen isotope data coupled with a CL study on carbonatite-related zircon. The CL pictures revealed that the zircon is broken and altered in the carbonatites and in associated syenites. Regarding geological field evidences of syenite-carbonatite relationship and the close agreement of published zircon U/Pb and whole rock and biotite K/Ar and Ar-Ar age data, the most probable process is early zircon crystallization from the syenite magma and late-stage reworking during magma evolution and carbonatite segregation. The oxygen isotope fractionations between zircon and other carbonatite minerals (calcite and pyroxene) support the assumption that the zircon would correspond to the early crystallization of syenite-carbonatite magmas.

The role of a transcrustal shear zone in orogenic gold mineralization at the Aijanahalli Mine, Dharwar Craton, South India

The Ajjanahalli gold mine is spatially associated with a Late Archean craton-scale shear zone in the eastern Chitradurga greenstone belt of the Dharwar craton, India. Gold mineralization is hosted by an similar to100-m-wide antiform in a banded iron formation. Original magnetite and siderite are replaced by a peak metamorphic alteration assemblage of chlorite, stilpnomelane, minnesotaite, sericite, ankerite, arsenopyrite, pyrite, pyrrhotite, and gold at ca. 300degrees to 350degreesC. Elements enriched in the banded iron formation include Ca, Mg, C, S, An, As, Bi. Cu, Sb, Zn, Pb, Se, Ag, and Te, whereas in the wall rocks As, Cu, Zn, Bi, Ag, and An are only slightly enriched. Strontium correlates with CaO, MgO, CO2, and As, which indicates cogenetic formation of arsenopyrite and Mg-Ca carbonates. The greater extent of alteration in the Fe-rich banded iron formation layers than in the wall rock reflects the greater reactivity of the banded iron formation layers. The ore fluids, as interpreted from their isotopic composition (delta(18)O = 6.5-8.5parts per thousand; initial Sr-87/Sr-86 = 0.7068-0.7078), formed by metamorphic devolatilization of deeper levels of the Chitradurga greenstone belt. Arsenopyrite, chalcopyrite, and pyrrhotite have delta(34)S values within a narrow range between 2.1 and 2.7 per mil, consistent with a sulfur source in Chitradurga greenstone belt lithologies. Based on spatial and temporal relationships between mineralization, local structure development, and sinistral strike-slip deformation in the shear zone at the eastern contact of the Chitradurga greenstone belt, we suggest that the Ajjanahalli gold mineralization formed by fluid infiltration into a low strain area within the first-order structure. The ore fluids were transported along this shear zone into relatively shallow crustal levels during lateral terrane accretion and a change from thrust to transcurrent tectonics. Based on this model of fluid flow, exploration should focus on similar low strain areas or potentially connected higher order splays of the first-order shear zone.

Insights into shallow magmatic processes in large silicic magma bodies: the trace element record in the Fish Canyon magma body, Colorado

Highly evolved rhyolite glass plus near-solidus mineral assemblages in voluminous, dacitic, crystal-rich ignimbrites provide an opportunity to evaluate the late magmatic evolution of granodiorite batholiths. This study reports laser-ablation ICP-MS analyses of trace element concentrations in feldspars, hornblende, biotite, titanite, zircon, magnetite, and interstitial glass of the crystal-rich Fish Canyon Tuff. The high-silica rhyolite glass is characterized by relatively high concentrations of feldspar-compatible elements (e.g., 100 ppm Sr and 500 ppm Ba) and low concentrations of Y (< 7 ppm) and HREE (&SIM; 1 ppm Yb), hence high LREE/HREE (Ce/Yb > 40) compared to many well-studied high-silica rhyolite glasses and whole-rock compositions. Most minerals record some trace element heterogeneities, with, in particular, one large hornblende phenocryst showing four- to six-fold core-to-rim increases in Sr and Ba coupled with a decrease in Sc. The depletions of Y and HREE in the Fish Canyon glass relative to the whole-rock composition (concentrations in glass &SIM; 30% of those in whole rocks) reflect late crystallization of phases wherein these elements were compatible. As garnet is not stable at the low-P conditions at which the Fish Canyon magma crystallized, we show that a combination of modally abundant hornblende (&SIM; 4%) + titanite (&SIM; 0.5-1%) and the highly polymerized nature of the rhyolitic liquid led to Y and HREE depletions in melt. Relatively high Sr and Ba contents in glass and rimward Sr and Ba increases in euhedral, concentrically zoned hornblende suggest partial feldspar dissolution and a late release of these elements to the melt as hornblende was crystallizing, in agreement with textural evidence for feldspar (and quartz) resorption. Both observations are consistent with thermal rejuvenation of the magma body prior to eruption, during which the proportion of melt increased via feldspar and quartz dissolution, even as hydrous and accessory phases were crystallizing. Sr/Y in Fish Canyon glass (13-18) is lower than the typical ``adakitic'' value (> 40), confirming that high Sr/Y is a reliable indicator of high-pressure magma generation and/or differentiation wherein garnet is implicated.

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.

The hypogene iron oxide copper-gold mineralization in the Mantoverde District, Northern Chile

The Mantoverde iron oxide copper-gold (IOCC) district, northern Chile, is known for its Cu production from supergene ores. Recently, exploration outlined an additional hypogene ore resource of 440 Mt with 0.56 percent Cu, and 0.12 g/t An. The hypogene sulfide mineralization occurs mainly as chalcopyrite and pyrite, typically in specularite or magnetite-cemented breccias and associated stockworks. The host rocks underwent variably intense K feldspar alteration, chloritization, sericitization, silicification, and/or carbonatization. A district scale Na(-Ca) alteration is absent. The IOCC mineralization in the district shows a strong tectonic control by northwest- to north-northwest-trending brittle structures. Large Cu sulfide-rich veins or Cu sulfide-cemented breccias are absent. Therefore, head grades of 4 percent Cu are an exception. There is a positive correlation between Cu and An grades. Gold is probably contained mostly in chalcopyrite and pyrite. Elevated concentrations of light rare-earth elements (LREE) occur locally but are attributed to redistribution of LREE within the deposits rather than to derivation from external sources. The Cu-Au ores in the Mantoverde district are low in and have relatively low contents in heavy metals that are potentially hazardous to the environment, such as As (avg 14 ppm), Hg (<5 ppm), or Cd (<0.2 ppm). The sulfur isotope ratios of chalcopyrite from the IOCC deposits lie between -5.6 and 8.9 per mil delta(34)S(VCDT). They show systematic variations within the district, which are interpreted to reflect relative distance to inferred fluid conduits and the level of deposition within the hydrothermal system. Most initial (87)Sr/(86)Sr values of altered volcanic rocks and hydrothermal calcite from the Mantoverde district are between 0.7031 and 0.7060 and are similar to those of the igneous rocks of the region. Lead isotope ratios of chalcopyrite are consistent with Pb (and by inference Cu) derived from Early Cretaceous magmatism. The sulfur, strontium, and lead isotope data of chalcopyrite, calcite gangue, or altered host rocks, respectively, are compatible with a genetic model that involves cooling of metal and sulfur-bearing magmatic-hydrothermal fluids that mix with meteoric waters or seawater at relatively shallow crustal levels. An additional exotic sulfur input is likely, though not required, for the copper mineralization. Apart from the IOCC. deposits, there are a number of smaller magnetite(-apatite) bodies in the district. These are geologically similar to the Cu-Au-bearing magnetite bodies, but are related to splays of the north-south-trending Atacama fault zone and differ in alteration and texture.

Oxygen isotope compositions of iron oxides from high-grade BIF-hosted iron ore deposits of the Central Hamersley Province, Western Australia: Constraints on the evolution of hydrothermal fluids

The Hamersley province of northwest Australia is one of the world's premier iron ore regions with high-grade martite-microplaty hematite iron ore deposits mostly hosted within banded iron formation (BIF) sequences of the Brockman Iron Formations of the Hamersley Group. These high-grade iron ores contain between 60 and 68 wt percent Fe, and formed by the multistage interaction of hydrothermal fluids with the host BIF formation. The oxygen isotope compositions of magnetite and hematite from BIF, hydrothermal alteration assemblages, and high-grade iron Ore were analyzed from the Mount Tom Price, Paraburdoo, and Charmar iron ore deposits. The delta(18)O values of magnetite and hematite from hydrothermal alteration assemblages and high-grade iron ore range from -9.0 to -2.9 per mil, a depletion of 5 to 15 per mil relative to the host BIF. The delta(18)O values are spatially controlled by faults within the deposits, a response to higher fluid flux and larger influence the isotopic compositions by the hydrothermal fluids. The oxygen isotope composition of hydrothermal fluids (delta(18)O(fluid)) indicates that the decrease in the (18)O content of iron oxides was due to the interaction of both basinal brines and meteoric fluids with the original BIF. Late-stage talc-bearing ore at the Mount Tom Price deposit formed in the presence of a pulse of delta(18)O-enriched basinal brine, indicating that hydrothermal fluids may have repeatedly interacted with the BIFs during the Paleoproterozoic.

The early Miocene rotation of the Corso-Sardinian block. New paleomagnetic constraints for the end of the motion

The paleomagnetic investigations carried out in the 70's on Oligo-Miocene volcanics of Sardinia have demonstrated that the island was turned by 35-30 degrees clockwise from 33 Ma up to 3-1-20.5 Ma and rotated counterclockwise in a few million years [De Jong et al., 1969, 1973; Bobier et Coulon, 1970; Coulon et al., 1974; Manzoni, 1974, 1975; Bellon rr nl.. 1977: Edel et Lortscher, 1977; Edel, 1979, 1980]. Since then, the end of the rotation fixed at 19 Ma by Montigny er al. [1981] was the subject of discussions and several studies associating paleomagnetism and radiometric dating were undertaken [Assorgia er al., 1994: Vigliotti et Langenheim, 1995: Deino et al., 1997; Gattacceca rt Deino, 1999]. This is a contribution to this debate that is hampered by thr important secular variation recorded in the volcanics. The only way to get our of this problem is to sample series of successive flows as completely as possible, and to reduce the effect of secular variation by the calculation of means. Sampling was performed north of Bonorva in 5 pyroclastic flows that belong to the upper ignimbritic series SI2 according to Coulon rr nl. [1974] or LBLS according to Assorgia et al. [1997] (fig. I). Ar-40/Ar-39 dating of biotites from the debris flow (MDF) has yielded an age or 18.35 +/- 0.03 Ma [Dubois, 2000]. Five of the investigated sites are located beneath the debris flow ITV, TVB, TVD, SPM85, SPM86), one site was cured in the matrix of the debris flow (MDF) and one in 4 metric blocks included in the flow (DFC). Another site was sampled in the upper ash flow (PDM) that marks the end of the pyroclastic activity, just before the marine transgression. According to micropaleontological and radiometric dating this transgression has occurred between 18.35 and 17.6 Ma [Dubois, 2000]. After removal of a soft viscous component, the thermal demagnetization generally shows a univectorial behaviour of the remanent magnetization (fig. 2a). The maximum unblocking temperatures of 580-620 degrees (tab. I) and a rapid saturation below 100 mT (fig. 3) indicate that the carrier of the characteristic magnetization is magnetite. The exception comes: from the upper site PDM in which were found two characteristic components, one with a normal polarity and low unblocking temperatures up to 350 degreesC and one with a reversed polarity and maximum unblocking temperatures at 580-600 degreesC of magnetite. After calculation of a mean direction for each flow, the mean << Al >> direction 4 degrees /57 degrees (alpha (95) = 13 degrees) computed with the mean directions for the 5 flows may be considered as weakly affected by secular variation. But the results require a more careful examination. The declinations are N to NNW beneath the debris flow. NNW in the debris flow. and NNE (or SSW) above the debris flow, The elongated distribution of the directions obtained at sites TVB and TVD. scattered from the mean direction of TV to the mean direction of MDF is interpreted as due to partial overprinting during the debris How volcanic episode, The low temperature component PDMa is likely related to the alteration seen on thin sections and is also viewed as an overprint. As NNE/SSW directions occur as well below (mean direction << B >> : 5 degrees /58 degrees) as above the debris flow (PDMb : 200 degrees/-58 degrees). the NNW directions (<< C >> : 337 degrees /64 degrees) associated with the debris flow volcanism may be interpreted as resulting from a magnetic field excursion. According to the polarity scale of Cande and Kent [1992, 1995] and the radiometric age of MDF, the directions with normal polarity (TV, TVB, TVD, SPM85. SPM86a. MDF. DFC) may represent the period 5En. while the directions with reversed polarity PDMb and SPM86b were likely acquired during the period 5Dr. Using the mean << Al >> direction, the mean << B >>, or the PDM direction (tab. I). the deviation in declination with the direction of stable Europe 6.4 degrees /58.7 degrees (alpha (95) = 8 degrees) for a selection of 4 middle Tertiary poles by Besse et Courtillot [1991] or 7 degrees /56 degrees (alpha (95) = 3 degrees) for 19 poles listed by Edel [1980] can be considered as negligible. Using the results from the uppermost ignimbritic layer of Anglona also emplaced around 18.3 Ma [Odin rt al.. 1994]. the mean direction << E >> (3 degrees /51.5 degrees) leads to the same conclusion. On the contrary, when taking into account all dated results available for the period 5En (mean direction << D >> 353 degrees /56 degrees for 45 sites) (tab. II). the deviation 13 degrees is much more significant. As the rotation of Sardinia started around 21-20.5 Ma. the assumption of a constant velocity of rotation and the deviations of the Sardinia directions with respect to the stable Europe direction locate the end of the motion between 18.3 and 17.2 or 16.7 Ma (fig. 4). During the interval 18.35-17.5 Ma, the marine transgression took place. At the same period a NE-SW shortening interpreted as resulting from the collision of Sardinia with Apulia affected different parts of the island [Letouzey et al., 1982]. Consequently, the new paleomagnetic results and the tectono-sedimentary evolution are in favour of an end of the rotation at 17.5-18 Ma.