Petrologia e geocronologia U-Pb do plúton granítico Serra da Rajada, porção central do domínio Rio Piranhas - Seridó, Província Borborema, NE do Brasil

The ediacaran plutonic activity related to the Brasilian/Pan-African orogeny is one of the most important geological features in the Borborema Province, represented along its extension by numerous batholiths, stocks, and dikes.The object of this study, the Serra Rajada Granitic Pluton (SRGP), located in the central portion of the Piranhas-Seridó River Domain is an example of this activity. This pluton has been the subject of cartographic, petrographic, geochronological and lithogeochemical studies and its rocks were characterized by two facies. First, the granitic facies were described as monzogranites consisting of K-feldspar, plagioclase (oligoclase - An23-24%), quartz and biotite (main mafic) and opaque minerals such as titanite, allanite, apatite, and zircon as accessories. Alteration minerals are chlorite, white mica and carbonate. Second, the dioritic facies consist of rocks formed by quartz diorite containing plagioclase (dominant mineral phase), quartz and K-feldspar. Biotite and amphibole are the dominant mafic minerals; and titanite, opaque minerals, allanite, zircon and apatite are the accessories. However, previous geological mapping work in the region also identified the presence of other lithostratigraphic units. These were described as gneisses and migmatites with undifferentiated amphibolite lenses related to the Caicó Complex (Paleoproterozoic) and metasedimentary rocks of the Seridó Group (Neoproterozoic) composed of paragneiss with calc-silicate lenses, muscovite quartzite and biotite schist (respectively, the Jucurutu formations, Equador and Seridó), the host rocks for the SRGP rocks. Leucomicrogranite and pegmatite dikes have also been identified, both related to the end of the Ediacaran magmatism and colluvial- eluvial and alluvial deposits related to Neogene and Quaternary, respectively. Lithogeochemical data on the SRGP granite facies, highlighted quite evolved rocks (SiO2 69% to 75%), rich in alkalis (Na2O+K2O ≥ 8.0%), depleted of MgO (≤ 0.45%), CaO (≤ 1.42%) and TiO2 (≤ 0.36%) and moderate levels of Fe2O3t (2.16 to 3.53%). They display transitional nature between metaluminous and peraluminous (predominance of the latter) with sub-alkaline/monzonitic (High K calcium-alkali) affinity. Harker diagrams show negative correlations for Fe2O3t, MgO, and CaO, indicating mafic and plagioclase fractionation. REE spectrum shows enrichment of LREE relative to heavy REE (LaN/YbN = 23.70 to 10.13), with negative anomaly in the Eu (Eu/Eu* = 0.70 to 0.23), suggesting fractionation or accumulation in the feldspars source (plagioclase). Data integration allows to correlate the SRGP rocks with those described as Calcium-Alkaline Suite of equigranular High K. The crystallization conditions of the SRGP rocks were determined from the integration of petrographic and lithogeochemical data. These data indicated intermediate to high conditions of ƒO2 (mineral paragenesis titanite + magnetite + quartz), parent magma saturated in H2O (early biotite crystallization), tardi-magmatic processes of fluids rich in ƒCO2, H2O and O2 causing part of the mineral assembly to change (plagioclase carbonation and saussuritization, biotite chloritization and opaques Sphenitization). Thermobarometrical conditions were estimated based on geochemical parameters (Zr and P2O5) and CIPW normative minerals, with results showing the liquidus minimum temperature of about800°C and the solidus temperature of approximately 700°C. The final/minimum crystallization pressure are suggested to be between 3 and 5 Kbar. The presence of zoned minerals (plagioclase and allanite) associated with lithogeochemical data in bi-log diagrams for Rb vs. Ba and Rb vs. Sr suggest the role of fractional crystallization as the dominant process in the magmatic evolution of SRGP. U-Pb Geochronological and Sm-Nd isotope studies indicated, respectively, the crystallization age of biotite monzogranite as 557 ± 13 Ma, with TDM model age of 2.36 Ga, and εNd value of -20.10 to the crystallization age, allowing to infer paleoproterozoic crustal source for the magma.

Petrologia e geocronologia U-Pb do plúton granítico Serra da Rajada, porção central do domínio Rio Piranhas - Seridó, Província Borborema, NE do Brasil

The ediacaran plutonic activity related to the Brasilian/Pan-African orogeny is one of the most important geological features in the Borborema Province, represented along its extension by numerous batholiths, stocks, and dikes.The object of this study, the Serra Rajada Granitic Pluton (SRGP), located in the central portion of the Piranhas-Seridó River Domain is an example of this activity. This pluton has been the subject of cartographic, petrographic, geochronological and lithogeochemical studies and its rocks were characterized by two facies. First, the granitic facies were described as monzogranites consisting of K-feldspar, plagioclase (oligoclase - An23-24%), quartz and biotite (main mafic) and opaque minerals such as titanite, allanite, apatite, and zircon as accessories. Alteration minerals are chlorite, white mica and carbonate. Second, the dioritic facies consist of rocks formed by quartz diorite containing plagioclase (dominant mineral phase), quartz and K-feldspar. Biotite and amphibole are the dominant mafic minerals; and titanite, opaque minerals, allanite, zircon and apatite are the accessories. However, previous geological mapping work in the region also identified the presence of other lithostratigraphic units. These were described as gneisses and migmatites with undifferentiated amphibolite lenses related to the Caicó Complex (Paleoproterozoic) and metasedimentary rocks of the Seridó Group (Neoproterozoic) composed of paragneiss with calc-silicate lenses, muscovite quartzite and biotite schist (respectively, the Jucurutu formations, Equador and Seridó), the host rocks for the SRGP rocks. Leucomicrogranite and pegmatite dikes have also been identified, both related to the end of the Ediacaran magmatism and colluvial- eluvial and alluvial deposits related to Neogene and Quaternary, respectively. Lithogeochemical data on the SRGP granite facies, highlighted quite evolved rocks (SiO2 69% to 75%), rich in alkalis (Na2O+K2O ≥ 8.0%), depleted of MgO (≤ 0.45%), CaO (≤ 1.42%) and TiO2 (≤ 0.36%) and moderate levels of Fe2O3t (2.16 to 3.53%). They display transitional nature between metaluminous and peraluminous (predominance of the latter) with sub-alkaline/monzonitic (High K calcium-alkali) affinity. Harker diagrams show negative correlations for Fe2O3t, MgO, and CaO, indicating mafic and plagioclase fractionation. REE spectrum shows enrichment of LREE relative to heavy REE (LaN/YbN = 23.70 to 10.13), with negative anomaly in the Eu (Eu/Eu* = 0.70 to 0.23), suggesting fractionation or accumulation in the feldspars source (plagioclase). Data integration allows to correlate the SRGP rocks with those described as Calcium-Alkaline Suite of equigranular High K. The crystallization conditions of the SRGP rocks were determined from the integration of petrographic and lithogeochemical data. These data indicated intermediate to high conditions of ƒO2 (mineral paragenesis titanite + magnetite + quartz), parent magma saturated in H2O (early biotite crystallization), tardi-magmatic processes of fluids rich in ƒCO2, H2O and O2 causing part of the mineral assembly to change (plagioclase carbonation and saussuritization, biotite chloritization and opaques Sphenitization). Thermobarometrical conditions were estimated based on geochemical parameters (Zr and P2O5) and CIPW normative minerals, with results showing the liquidus minimum temperature of about800°C and the solidus temperature of approximately 700°C. The final/minimum crystallization pressure are suggested to be between 3 and 5 Kbar. The presence of zoned minerals (plagioclase and allanite) associated with lithogeochemical data in bi-log diagrams for Rb vs. Ba and Rb vs. Sr suggest the role of fractional crystallization as the dominant process in the magmatic evolution of SRGP. U-Pb Geochronological and Sm-Nd isotope studies indicated, respectively, the crystallization age of biotite monzogranite as 557 ± 13 Ma, with TDM model age of 2.36 Ga, and εNd value of -20.10 to the crystallization age, allowing to infer paleoproterozoic crustal source for the magma.

Geochemistry, and Nd- and Pb-isotopic composition of basalts from the upper oceanic crust of the Costa Rica Rift

The DSDP/ODP Hole 504B, drilled in the 5.9 Ma southern flank of the Costa Rica Rift, represents the deepest section through modern ocean floor basaltic basement. The hole penetrates a 570 m thick volcanic zone, a 210 m thick transition zone of volcanic rocks and dykes, and 1056 m of dykes. A representative selection of these basalt types has been investigated with respect to Nd and Pb isotopes. The epsilonNd of the basalts varies from 7.62 to 11.16. This range in the Nd-isotope composition represents about 67% of the total range reported for Pacific MORB. The Pb-isotope composition also shows significant variation, with 206Pb/204Pb varying from 17.90 to 18.82. The isotopic data show that a small volume of enriched mantle existed in the source. The large ranges in isotopic composition in a single drill hole demonstrate the importance of small-scale mantle heterogeneities in the petrogenesis of MORB. Fractional melting and extraction of small magma batches by channelled flow, and small, short-lived crustal magma reservoirs, with limited potential for mixing of the mantle derived magmas, are favored by these isotopic data.

Metallic glass fiber-reinforced Zr-based bulk metallic glass

A novel Zr-based bulk metallic glass composite was fabricated using stainless steel capillaries as the reinforcement. Large plasticity (14%) was achieved in the composite with a reinforcement volume fraction of 38%. The high plasticity observed can be attributed to the formation of small glass fibers encapsulated by the steel capillaries, which promotes multiple shear bands in both metallic glass matrix and the fibers themselves. A new parameter was also proposed to approximately evaluate the reinforcement efficiency.

A vibrational spectroscopic study of the mineral hinsdalite (Pb,Sr)Al3(PO4)(SO4)(OH)6

The objective of this research is to determine the molecular structure of the mineral hinsdalite using vibrational spectroscopy. The mineral hinsdalite (Pb,Sr)Al3(PO4,SO4)2(OH)6 is a hydroxy phosphate-sulphate mineral belonging to the beudantite subgroup of alunites. The mineral is interesting because it contains two oxyanions, phosphate and sulphate, which is unusual. The formation of hinsdalite offers a mechanism for the removal of phosphate from the environment. The mineral has been characterised by Raman spectroscopy and infrared spectroscopy. The spectra are then related to the molecular structure of the mineral. Bands at various wavenumbers are assigned to the different vibrational modes of hinsdalite, which were then associated to the molecular structure of the mineral. Bands were primarily assigned to phosphate and sulphate stretching and bending modes. The Raman spectrum is characterised by an intense sharp band at 982 cm-1 with a component band at 997 cm-1 assigned to the ν1 (PO4)3- symmetric stretching modes. Two symmetric stretching modes for both phosphate and sulphate supported the concept of non-equivalent phosphate and sulphate units in the mineral structure. Bands in the OH stretching region enabled hydrogen bond distances to be calculated. Hinsdalite is characterised by disordered phosphate/sulphate tetrahedra and non-equivalent phosphate units are observed in the vibrational spectrum of hinsdalite.

Raman spectroscopy of selected tsumcorite Pb(Zn,Fe3+)2(AsO4)2(OH,H2O) minerals –implications for arsenate accumulation

The presence of arsenic in the environment is a hazard. The accumulation of arsenate by a range of cations in the formation of minerals provides a mechanism for the accumulation of arsenate. The formation of the tsumcorite minerals is an example of a series of minerals which accumulate arsenate. There are about twelve examples in this mineral group. Raman spectroscopy offers a method for the analysis of these minerals. The structure of selected tsumcorite minerals with arsenate and sulphate anions were analysed by Raman spectroscopy. Isomorphic substitution of sulphate for arsenate is observed for gartrellite and thometzekite. A comparison is made with the sulphate bearing mineral natrochalcite. The position of the hydroxyl and water stretching vibrations are related to the strength of the hydrogen bond formed between the OH unit and the AsO43- anion. Characteristic Raman spectra of the minerals enable the assignment of the bands to specific vibrational modes.

Tracking the magmatic evolution of island arc volcanism : insights from a high-precision Pb isotope record of Montserrat, Lesser Antilles

The volcanic succession on Montserrat provides an opportunity to examine the magmatic evolution of island arc volcanism over a ∼2.5 Ma period, extending from the andesites of the Silver Hills center, to the currently active Soufrière Hills volcano (February 2010). Here we present high-precision double-spike Pb isotope data, combined with trace element and Sr-Nd isotope data throughout this period of Montserrat's volcanic evolution. We demonstrate that each volcanic center; South Soufrière Hills, Soufrière Hills, Centre Hills and Silver Hills, can be clearly discriminated using trace element and isotopic parameters. Variations in these parameters suggest there have been systematic and episodic changes in the subduction input. The SSH center, in particular, has a greater slab fluid signature, as indicated by low Ce/Pb, but less sediment addition than the other volcanic centers, which have higher Th/Ce. Pb isotope data from Montserrat fall along two trends, the Silver Hills, Centre Hills and Soufrière Hills lie on a general trend of the Lesser Antilles volcanics, whereas SSH volcanics define a separate trend. The Soufrière Hills and SSH volcanic centers were erupted at approximately the same time, but retain distinctive isotopic signatures, suggesting that the SSH magmas have a different source to the other volcanic centers. We hypothesize that this rapid magmatic source change is controlled by the regional transtensional regime, which allowed the SSH magma to be extracted from a shallower source. The Pb isotopes indicate an interplay between subduction derived components and a MORB-like mantle wedge influenced by a Galapagos plume-like source.

The effects of low degree alteration on Sm-Nd and U-Pb isotope systematics in Eoarchean basalts from the Doolena Gap and Warralong Greenstone belts, Pilbara Craton, Western Australia

This research led to the discovery of one of the best preserved remnants of the Earth's surficial environment 3.47 billion years ago. These ancient volcanic and sedimentary rocks contain original minerals and textures that are rare in rocks of this age. The research concentrated on chemical analysis of volcanic rocks to differentiate secondary alteration from the primary magmatic signature. This study contributes to our understanding of melting processes and geochemical reservoirs in the early Earth, which is vital for forward modelling of Earth's geodynamic evolution.

Electrocatalytic and SERS activity of Pt rich Pt-Pb nanostructures formed via the utilisation of in-situ underpotential deposition of lead

The controlled synthesis of nanostructured materials remains an ongoing area of research, especially as the size, shape and composition of nanomaterials can greatly influence their properties and applications. In this work we present the electrodeposition of highly dendritic platinum rich platinum-lead nanostructures, where lead acetate acts as an inorganic shape directing agent via underpotential deposition on the growing electrodeposit. It was found that these nanomaterials readily oxidise at potentials below monolayer oxide formation, which significantly impacts on the methanol electrooxidation reaction and correlates with the incipient hydrous oxide adatom mediator (IHOAM) model of electrocatalysis. Additionally these materials were tested for their surface enhanced Raman scattering (SERS) activity, where the high density of sharp tips provides promise for their application as SERS substrates.

A vibrational spectroscopic study of the silicate mineral normandite – NaCa(Mn2+,Fe2+)(Ti,Nb,Zr)Si2O7(O,F)2

We have studied the mineral normandite using a combination of scanning electron microscopy with energy dispersive spectroscopy and vibrational spectroscopy. The mineral normandite NaCa(Mn2+,Fe2+)(Ti,Nb,Zr)Si2O7(O,F)2 is a crystalline sodium calcium silicate which contains rare earth elements. Chemical analysis shows the mineral contains a range of elements including Na, Mn2+, Ca, Fe2+ and the rare earth element niobium. No Raman bands are observed above 1100 cm−1. The mineral is characterised by Raman bands observed at 724, 748, 782 and 813 cm−1. Infrared bands are broad; nevertheless bands may be resolved at 723, 860, 910, 958, 933, 1057 and 1073 cm−1. Intense Raman bands at 454, 477 and 513 cm−1 are attributed to OSiO bending modes. No Raman bands are observed in the hydroxyl stretching region, but low intensity infrared bands are observed at 3191 and 3450 cm−1. This observation brings into question the true formula of the mineral.

Geochronological (U–Pb, U–Th–total Pb, Sm–Nd) and geochemical (REE, 87Sr/86Sr, δ18O, δ13C) tracing of intraplate tectonism and associated fluid flow in the Warburton Basin, Australia

The Warburton Basin of central Australia has experienced a complex tectonic and fluid-flow history, resulting in the formation of various authigenic minerals. Geochemical and geochronological analyses were undertaken on vein carbonates from core samples of clastic sediments. Results were then integrated with zircon U–Pb dating and uraninite U–Th–total Pb dating from the underlying granite. Stable and radiogenic isotopes (δ18O, Sr and εNd), as well as trace element data of carbonate veins indicate that >200 °C basinal fluids of evolved meteoric origin circulated through the Warburton Basin. Almost coincidental ages of these carbonates (Sm–Nd; 432 ± 12 Ma) with primary zircon (421 ± 3.8 Ma) and uraninite (407 ± 16 Ma) ages from the granitic intrusion point towards a substantial period of active tectonism and an elevated thermal regime during the mid Silurian. We hypothesise that such a thermal regime may have resulted from extensional tectonism and concomitant magmatic activity following regional orogenesis. This study shows that the combined application of geochemical and geochronological analyses of both primary and secondary species may constrain the timing of tectonomagmatic events and associated fluid flow in intraplate sedimentary basins. Furthermore, this work suggests that the Sm–Nd-isotopic system is surprisingly robust and can record geologically meaningful age data from hydrothermal mineral species.

Glass forming ability and stability: Ternary Cu bearing Ti, Zr, Hf alloys

Four Cu bearing alloys of nominal composition Zr25Ti25Cu50, Zr34Ti16Cu50, Zr25Hf25Cu50 and Ti25Hf25Cu50 have been rapidly solidified in order to produce ribbons. All the alloys become amorphous after meltspinning. In the Zr34Ti16Cu50 alloy localized precipitation of cF24 Cu5Zr phase can be observed in the amorphous matrix. The alloys show a tendency of phase separation at the initial stages of crystallization. The difference in crystallization behavior of these alloys with Ni bearing ternary alloys can be explained by atomic size, binary heat of mixing and Mendeleev number. It has been observed that both Laves and Anti-Laves phase forming compositions are suitable for glass formation. The structures of the phases, precipitated during rapid solidification and crystallization can be viewed in terms of Bernal deltahedra and Frank-Kasper polyhedra.