Geochemical composition of sulfide and oxide minerals from ODP Sites 193-1188 and 193-1189, PACMANUS field

Ocean Drilling Program (ODP) Leg 193 recovered core from the active PACMANUS hydrothermal field (eastern Manus Basin, Papua New Guinea) that provided an excellent opportunity to study mineralization related to a seafloor hydrothermal system hosted by felsic volcanic rocks. The purpose of this work is to provide a data set of mineral chemistry of the sulfide-oxide mineralization and associated gold occurrence in samples drilled at Sites 1188 and 1189. PACMANUS consists of five active vent sites, namely Rogers Ruins, Roman Ruins, Satanic Mills, Tsukushi, and Snowcap. In this work two sites were studied: Snowcap and Roman Ruins. Snowcap is situated in a water depth of 1670 meters below sea level [mbsl], covers a knoll of dacite-rhyodacite lava, and is characterized by low-temperature diffuse venting. Roman Ruin lies in a water depth of 1693-1710 mbsl, is 150 m across, and contains numerous large, active and inactive, columnar chimneys. Sulfide mineralogy at the Roman Ruins site is dominated by pyrite with lesser amounts of chalcopyrite, sphalerite, pyrrhotite, marcasite, and galena. Sulfide minerals are relatively rare at Snow Cap. These are dominated by pyrite with minor chalcopyrite and sphalerite and traces of pyrrhotite. Native gold has been found in a single sample from Hole 1189B (Roman Ruins). Oxide minerals are represented by Ti magnetite, magnetite, ilmenite, hercynite (Fe spinel), and less abundant Al-Mg rich chromite (average = 10.6 wt% Al2O3 and 5.8 wt% MgO), Fe-Ti oxides, and a single occurrence of pyrophanite (Mn Ti O3). Oxide mineralization is more developed at Snowcap, whereas sulfide minerals are more extensive and show better development at Roman Ruins. The mineralogy was obtained mainly by a detailed optical microscopy study. Oxide mineral identifications were confirmed by X-ray diffraction, and mineral chemistry was determined by electron probe microanalyses.

The Evolution of the Los Negritos Porphyry Copper Deposit, Coquimbo, Chile: Geological, Geochronological, Mineralogical and Geochemical Evidence

The Los Negritos porphyry copper deposit is located ~ 4 km to the northeast of Carmen de Andacollo Mine in the Chilean Cretaceous metallogenic belt. The mineralization is hosted in andesite of the Quebrada Marquesa Formation and a series of at least four early to intramineral porphyry intrusive rock types: plagioclase quartz biotite porphyry (P1b and P1a dated at 109.60± 0.75 Ma and 107.22± 0.40 Ma); plagioclase biotite porphyry (P2: 106.30 ± 0.47 Ma); and quartz plagioclase biotite porphyry (P3: 106.19 ± 0.42 Ma). These units are cut by late‐ to post‐mineral plagioclase‐hornblende porphyritic rocks (P4b: 106.20 ± 0.69 Ma and P4a: 106.50 ± 0.68 Ma). The earliest intrusive units (P1) were affected by an initial stage of K‐feldspar‐biotite alteration, with chalcopyrite, molybdenite (date at 108.5 ± 0.5 Ma) and gold (up to 0.11 ppm), and the surrounding volcanic host rock was overprinted by chlorite‐epidote dominated (propylitic) alteration. Subsequent to the P2 and P3 intrusion, these rocks were affected by albite and then a second stage of potassic alteration. The Ti and Ba contents in hydrothermal biotite are notably lower (typically Ti = 0.100‐0.144 a.p.f.u. and Ba = 0.001‐0.005 a.p.f.u) than in magmatic ones (generally Ti = 0.186‐0.222 a.p.f.u. and Ba = 0.014‐0.023 a.p.f.u.), and constitute an excellent discriminant of the nature of biotite. These early stages of alteration were overprinted by copper‐molybdenum bearing chlorite‐sericite alteration at 106.60 ± 0.5 Ma (Re‐Os age in molybdenite) and by quartz‐sericite‐pyrite veins (phyllic), respectively in the southwest and northeast areas. The average temperature associated with these two alteration facies is estimated around 305 °C. Weak albite‐calcite alteration, spatially associated with sulfosalts and distributed along the margins of P3, overprinted the phyllic facies. The intrusive rock units at the Los Negritos and Carmen de Andacollo deposits are geochemically classified as diorite to granodiorite with a calc‐alkaline magmatic affinity, and formed in a volcanic arc setting from partial melting of a metasomatized mantle wedge. They are interpreted to be cogenetic, and related to a common long‐lived magma chamber that emplaced during a period of tectonic inversion known as the Subhercynian, Peruvian or Pacific event.

Concrete deterioration due to sulfide-bearing aggregates

Dans la région de Trois-Rivières (Québec, Canada), plus de 1 000 bâtiments résidentiels et commerciaux montrent de graves problèmes de détérioration du béton. Les problèmes de détérioration sont liés à l’oxydation des sulfures de fer incorporés dans le granulat utilisé pour la confection du béton. Ce projet de doctorat vise à mieux comprendre les mécanismes responsables de la détérioration de béton incorporant des granulats contenant des sulfures de fer, et ce afin de développer une méthodologie pour évaluer efficacement la réactivité potentielle de ce type de granulats. Un examen pétrographique détaillé de carottes de béton extraites de fondations résidentielles montrant différents degré d’endommagement a été réalisé. Le granulat problématique contenant des sulfures de fer a été identifié comme un gabbro à hypersthène incorporant différentes proportions (selon les différentes localisations dans les deux carrières d’origine) de pyrrhotite, pyrite, chalcopyrite et pentlandite. Les produits de réaction secondaires observés dans les échantillons dégradés comprennent des formes minérales de "rouille", gypse, ettringite et thaumasite. Ces observations ont permis de déterminer qu’en présence d’eau et d’oxygène, la pyrrhotite s’oxyde pour former des oxyhydroxides de fer et de l’acide sulfurique qui provoquent une attaque aux sulfates dans le béton. Tout d’abord, la fiabilité de l’approche chimique proposée dans la norme européenne NF EN 12 620, qui consiste à mesurer la teneur en soufre total (ST,% en masse) dans le granulat pour détecter la présence (ou non) de sulfures de fer, a été évaluée de façon critique. Environ 50% (21/43) des granulats testés, représentant une variété de types de roches/lithologies, a montré une ST > 0,10%, montrant qu’une proportion importante de types de roches ne contient pas une quantité notable de sulfure, qui, pour la plupart d’entre eux, sont susceptibles d’être inoffensifs dans le béton. Ces types de roches/granulats nécessiteraient toutefois d’autres tests pour identifier la présence potentielle de pyrrhotite compte tenu de la limite de ST de 0,10 % proposée dans les normes européennes. Basé sur une revue exhaustive de la littérature et de nombreuses analyses de laboratoire, un test accéléré d’expansion sur barres de mortier divisé en deux phases a ensuite été développé pour reproduire, en laboratoire, les mécanismes de détérioration observés à Trois-Rivières. Le test consiste en un conditionnement de 90 jours à 80°C/80% RH, avec 2 cycles de mouillage de trois heures chacun, par semaine, dans une solution d’hypochlorite de sodium (eau de javel) à 6% (Phase I), suivi d’une période pouvant atteindre 90 jours de conditionnement à 4°C/100 % HR (Phase II). Les granulats ayant un potentiel d’oxydation ont présenté une expansion de 0,10 % au cours de la Phase I, tandis que la formation potentielle de thaumasite est détectée par le regain rapide de l’expansion suivi par la destruction des échantillons durant la Phase II. Un test de consommation d’oxygène a également été modifié à partir d’un test de Drainage Minier Acide, afin d’évaluer quantitativement le potentiel d’oxydation des sulfures de fer incorporés dans les granulats à béton. Cette technique mesure le taux de consommation d’oxygène dans la partie supérieure d’un cylindre fermé contenant une couche de matériau compacté afin de déterminer son potentiel d’oxydation. Des paramètres optimisés pour évaluer le potentiel d’oxydation des granulats comprennent une taille de particule inférieure à 150 μm, saturation à 40 %, un rapport de 10 cm d’épaisseur de granulat par 10 cm de dégagement et trois heures d’essai à 22ᵒC. Les résultats obtenus montrent que le test est capable de discriminer les granulats contenant des sulfures de fer des granulats de contrôle (sans sulfures de fer) avec un seuil limite fixé à 5% d’oxygène consommé. Finalement, un protocole d’évaluation capable d’estimer les effets néfastes potentiels des granulats à béton incorporant des sulfures de fer a été proposé. Le protocole est divisé en 3 grandes phases: (1) mesure de la teneur en soufre total, (2) évaluation de la consommation d’oxygène, et (3) un test accéléré d’expansion sur barres de mortier. Des limites provisoires sont proposées pour chaque phase du protocole, qui doivent être encore validées par la mise à l’essai d’un plus large éventail de granulats.

Growth and application of planar III-V semiconductor nanowires grown with MOCVD

The semiconductor nanowire has been widely studied over the past decade and identified as a promising nanotechnology building block with application in photonics and electronics. The flexible bottom-up approach to nanowire growth allows for straightforward fabrication of complex 1D nanostructures with interesting optical, electrical, and mechanical properties. III-V nanowires in particular are useful because of their direct bandgap, high carrier mobility, and ability to form heterojunctions and have been used to make devices such as light-emitting diodes, lasers, and field-effect transistors. However, crystal defects are widely reported for III-V nanowires when grown in the common out-of-plane <111>B direction. Furthermore, commercialization of nanowires has been limited by the difficulty of assembling nanowires with predetermined position and alignment on a wafer-scale. In this thesis, planar III-V nanowires are introduced as a low-defect and integratable nanotechnology building block grown with metalorganic chemical vapor deposition. Planar GaAs nanowires grown with gold seed particles self-align along the <110> direction on the (001) GaAs substrate. Transmission electron microscopy reveals that planar GaAs nanowires are nearly free of crystal defects and grow laterally and epitaxially on the substrate surface. The nanowire morphology is shown to be primarily controlled through growth temperature and an ideal growth window of 470 +\- 10 °C is identified for planar GaAs nanowires. Extension of the planar growth mode to other materials is demonstrated through growth of planar InAs nanowires. Using a sacrificial layer, the transfer of planar GaAs nanowires onto silicon substrates with control over the alignment and position is presented. A metal-semiconductor field-effect transistor fabricated with a planar GaAs nanowire shows bulk-like low-field electron transport characteristics with high mobility. The aligned planar geometry and excellent material quality of planar III-V nanowires may lead to highly integrated III-V nanophotonics and nanoelectronics.

Reduced graphene oxide wrapped Cu2O supported on C3N4: An efficient visible light responsive semiconductor photocatalyst

Herein, Cu 2O spheres were prepared and encapsulated with reduced graphene oxide (rGO). The Cu 2O–rGO–C3N4 composite covered the whole solar spectrum with significant absorption intensity. rGO wrapped Cu 2O loading caused a red shift in the absorption with respect to considering the absorption of bare C3N4. The photoluminescence study confirms that rGO exploited as an electron transport layer at the interface of Cu 2O and C3N4 heterojunction. Utmost, ∼2 fold synergistic effect was achieved with Cu 2O–rGO–C3N4 for the photocatalytic reduction of 4-nitrophenol to 4-aminophenol in comparison with Cu 2O–rGO and C3N4. The Cu 2O–rGO–C3N4 photocatalyst was reused for four times without loss in its activity.

Geologia, petrologia, geocronologia e mineralizações sulfetadas do complexo ézio, província mineral de carajás, Brasil

Dissertação (mestrado)—Universidade de Brasília, Instituto de Geociências, Pós-Graduação em Geologia, 2015.

Hall Effect and transient surface photovoltage (SPV) study of Cu3BiS3 thin films

Se presentan las propiedades eléctricas del compuesto Cu3BiS3 depositado por co-evaporación. Este es un nuevo compuesto que puede tener propiedades adecuadas para ser utilizado como capa absorbente en celdas solares. Las muestras fueron caracterizadas a través de medidas de efecto Hall y fotovoltaje superficial transiente (SPV). A través de medidas de efecto Hall se encontró que la concentración de portadores de carga n es del orden de 1016 cm-3 independiente de la relación de masas de Cu/Bi. También se encontró que la movilidad de este compuesto (μ del orden de 4 cm2V -1s-1) varía de acuerdo con los mecanismos de transporte que la gobiernan en dependencia con la temperatura. A partir de las medidas de SPV se encontró alta densidad de defectos superficiales, defectos que son pasivados al superponer una capa buffer sobre el compuesto Cu3BiS3.

Study of heterostructures of Cu3BiS3–buffer layer measured by Kelvin probe force microscopy measurements (KPFM)

The interface formed between Cu3BiS3 thin films and the buffer layer is a potentially limiting factor to the performance of solar cells based on Al/Cu3BiS3/buffer heterojunctions. The buffer layers of ZnS and In2S3 were grown by coevaporation, and tested as an alternative to the traditional CdS deposited by chemical bath deposition. From the Kelvin probe force microscopy measurements, we found the values of the work function of ZnS, In2S3, and CdS, layers deposited into Cu3BiS3. Additionally, different electronic activity was found for different grain boundaries (GBs), from studies under illumination, we also found the net doping concentration and the density of charged GB states for Cu3BiS3 and Cu3BiS3/CdS.