Temperature Dependence of the Intergranular Critical Current Density in Uniaxially Pressed Bi(1.65)Pb(0.35)Sr(2)Ca(2)Cu(3)O(10+delta) Samples

We have studied the normal and superconducting transport properties of Bi(1.65)Pb(0.35)Sr(2)Ca(2)Cu(3)O(10+delta) (Bi-2223) ceramic samples. Four samples, from the same batch, were prepared by the solid-state reaction method and pressed uniaxially at different compacting pressures, ranging from 90 to 250 MPa before the last heat treatment. From the temperature dependence of the electrical resistivity, combined with current conduction models for cuprates, we were able to separate contributions arising from both the grain misalignment and microstructural defects. The behavior of the critical current density as a function of temperature at zero applied magnetic field, J (c) (T), was fitted to the relationship J (c) (T)ae(1-T/T (c) ) (n) , with na parts per thousand 2 in all samples. We have also investigated the behavior of the product J (c) rho (sr) , where rho (sr) is the specific resistance of the grain-boundary. The results were interpreted by considering the relation between these parameters and the grain-boundary angle, theta, with increasing the uniaxial compacting pressure. We have found that the above type of mechanical deformation improves the alignment of the grains. Consequently the samples exhibit an enhance in the intergranular properties, resulting in a decrease of the specific resistance of the grain-boundary and an increase in the critical current density.

Influence of pH on the incorporation and growth of Pb(2)CrO(5) crystallites in silica matrix

Pb(2)CrO(5) nanoparticles were embedded in an amorphous SiO(2) matrix by the sol-gel process. The pH and heat treatment effects were evaluated in terms of structural, microstructural and optical properties from Pb(2)CrO(5)/SiO(2) compounds. X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), energy dispersive spectroscopy (EDS), and diffuse reflectance techniques were employed. Kubelka-Munk theory was used to calculate diffuse reflectance spectra that were compared to the experimental results. Finally, colorimetric coordinates of the Pb(2)CrO(5)/SiO(2) compounds were shown and discussed. In general, an acid pH initially dissolves Pb(2)CrO(5) nanoparticles and following heat treatment at 600 A degrees C crystallized into PbCrO(4) composition with grain size around 6 nm in SiO(2) matrix. No Pb(2)CrO(5) solubilization was observed for basic pH. These nanoparticles were incorporated in silica matrix showing a variety of color ranging from yellow to orange.

Combined Crystallographic and Solution Molecular Dynamics Study of Allosteric Effects in Ester and Ketone p-tert-Butylcalix[4]arene Derivatives and Their Complexes with Acetonitrile, Cd(II), and Pb(II)

We describe here a procedure to bridge the gap in the field of calixarene physicochemistry between solid-state atomic-resolution structural information and the liquid-state low-resolution thermodynamics and spectroscopic data. We use MD simulations to study the kinetics and energetics involved in the complexation of lower rim calix[4]arene derivatives (L), containing bidentate ester (1) and ketone (2) pendant groups, with acetonitrile molecule (MeCN) and Cd2+ and Pb2+ ions (M2+) in acetonitrile solution. On one hand, we found that the prior inclusion of MeCN into the calix to form a L(MeCN) adduct has only a weak effect in preorganizing the hydrophilic cavity toward metal ion binding. On the other hand, the strong ion-hydrophilic cavity interaction produces a wide open calix which enhances the binding of one MeCN molecule (allosteric effect) to stabilize the whole (M2+)1(MeCN) bifunctional complex. We reach two major conclusions: (i) the MD results for the (M2+)1(MeCN) binding are in close agreement with the ""endo"", fully encapsulated, metal complex found by X-ray diffraction and in vacuo MD calculations, and (ii) the MD structure for the more flexible 2 ligand, however, differs from the also endo solid-state molecule. In fact, it shows strong solvation effects at the calixarene lower bore by competing MeCN molecules that share the metal coordination sphere with the four C=O oxygens of an ""exo"" (M2+)2(MeCN) complex.

Lead and aluminum bonding in Pb-Al metaphosphate glasses

The bonding properties of cations in phosphate glasses determine many short- and medium-range structural features in the glass network, hence influencing bulk properties. In this work, Pb-Al-metaphosphate glasses (1 - x)Pb-(PO(3))(2)center dot xAI(PO(3))(3) with 0 <= - x <= 1 were analyzed to determine the effect of the substitution of Pb by Al on the glass structure in the metaphosphate composition. The glass transition temperature and density were measured as a function of the Al concentration. The vibrational and structural properties were probed by Raman spectroscopy and nuclear magnetic resonance of (31)P, (27)Al, and (207)Pb. Aluminum incorporates homogeneously in the glass creating a stiffer and less packed network. The average coordination number for Al decreases from 5.9 to 5.0 as x increases from 0.1 to 1, indicating more covalent Al-O bonds. The coordination number of Pb in these glasses is greater than 8, showing an increasing ionic behavior for compositions richer in Al. A quantitative analysis of the phosphate speciation shows definite trends in the bonding of AlO(n) groups and phosphate tetrahedra. In glasses with x < 0.48, phosphate groups share preferentially only one nonbridging O corner with an AlO(n) coordination polyhedron. For x > 0.48 more than one nonbridging O can be linked to AlO(n) polyhedra. There is no corner sharing of O between AlO(n) and PbO(n) polyhedra nor between AlO(n) themselves throughout the compositional range. The PbO(n) coordination polyhedra show considerable nonbridging O sharing, with each O participating in the coordination sphere of at least two Pb. The bonding preferences determined for Al are consistent with the behavior observed in Na-Al and Ca-Al metaphosphates, indicating this may be a general behavior for ternary phosphate glasses.

Precambrian history of the Zona Transversal of the Borborema Province, NE Brazil: Insights from Sm-Nd and U-Pb geochronology

The Borborema Province has three major subprovinces. The northern subprovince lies north of the Patos shear zone and is comprised of Paleoproterozoic cratonic basement with Archean nuclei, plus overlying Neoproterozoic supracrustal rocks and Brasiliano plutonic rocks. The central subprovince occurs between the Patos and Pernambuco shear zones and is mainly comprised of the Zona Transversal. The southern subprovince occurs between the Pernamabuco shear zone and the Sao Francisco craton and is comprised of a tectonic collage of various blocks, terranes, or domains ranging in age from Archean to Neoproterozoic. This report focuses on the Zona Transversal, especially on Brasiliano rocks for which we have the most new information. Paleoproterozoic gneisses with ages of 2.0-2.2 Ga occur discontinuously throughout the Zona Transversal. The Cariris Velhos suite consists of metavolcanic, metasedimentary, and metaplutonic rocks yielding U-Pb zircon ages of 995-960 Ma. This suite is mainly confined to a 100 km wide belt that extends for more than 700 km within the Alto Pajeu terrane. Sm-Nd model ages in metaigneous rocks cluster about 1.3-1.6 Ga, indicating that older crust was involved in genesis of their magmas. Brasiliano supracrustal rocks dominate the Pianco-Alto Brigida terrane, and they probably also constitute significant parts of the Alto Pajeu and Rio Capibaribe terranes. They are only slightly older than early stages of Brasiliano plutonism, with detrital zircon ages at least as young as 620 Ma; most T(DM) ages range from 1.2 to 1.6 Ga. Brasiliano plutons range from ca. 640 to 540 Ma, and their T(DM) ages range from 1.2 to 2.5 Ga. Previous workers have shown significant correlations among U-Pb ages, Sm-Nd model ages, petrology, and geochemistry, and we are able to reinforce and extend these correlations. Stage I plutons formed 640 -610 Ma and have T(DM) ages less than 1.5 Ga. Stage 11 (610-590 Ma) contains few plutons, but coincides with the peak of compressional deformation, metamorphism, and formation of migmatites. Stage III plutons (590 to ca. 575 Ma) have older T(DM) ages (ca. 1.8-2.0 Ga), as do Stage IV plutons (575 to ca. 550 Ma; T(DM) from 1.9 to 2.4 Ga). Stage III plutons formed during the transition from compressional to transcurrent deformation, while Stage IV plutons are mainly post-tectonic. Stage V plutons (550-530 Ma) are commonly undeformed (except along younger shear zones) and have A-type geochemistry. The five stages have distinct geochemical properties, which suggest that the tectonic settings evolved from early, arc-related magma-genesis (Stage I) to within-plate magma-genesis (Stage V), with perhaps some intermediate phases of extensional environments. (C) 2011 Elsevier Ltd. All rights reserved.

30 million years of Permian volcanism recorded in the Choiyoi igneous province (W Argentina) and their source for younger ash fall deposits in the Parana Basin: SHRIMP U-Pb zircon geochronology evidence

We present four SHRIMP U-Pb zircon ages for the Choiyoi igneous province from the San Rafael Block, central-western Argentina. Dated samples come from the Yacimiento Los Reyunos Formation (281.4 +/- 2.5 Ma) of the Cochico Group (Lower Choiyoi section: andesitic breccias, dacitic to rhyolitic ignimbrites and continental conglomerates). Agua de los Burros Formation (264.8 +/- 2.3 Ma and 264.5 +/- 3.0 Ma) and Cerro Carrizalito Formation (251.9 +/- 2.7 Ma Upper Choiyoi section: rhyolitic ignimbrites and pyroclastic flows) spanning the entire Permian succession of the Choiyoi igneous province. A single ziron from the El Imperial Formation, that is overlain unconformably by the Choiyoi succession, yielded an early Permian age (297.2 +/- 5.3 Ma). while the main detrital zircon population indicated an Ordovician age (453.7 +/- 8.1 Ma). The new data establishes a more precise Permian age (Artinskian-Lopingian) for the section studied spanning 30 Ma of volcanic activity. Volcanological observations for the Choiyoi succession support the occurrence of explosive eruptions of plinian to ultraplinian magnitudes, capable of injecting enormous volumes of tephra in the troposphere-stratosphere. The new SHRIMP ages indicate contemporaneity between the Choyoi succession and the upper part of the Parana Basin late Paleozoic section, from the Irad up to the Rio do Rasto formations, encompassing about 24 Ma. Geochemical data show a general congruence in compositional and tectonic settings between the volcanics and Parana Basin Permian ash fall derived layers of bentonites. Thickness and granulometry of ash fall layers broadly fit into the depletion curve versus distance from the remote source vent of ultraplinian eruptions. Thus, we consider that the Choiyoi igneous province was the source of ash fall deposits in the upper Permian section of the Parana Basin. Data presented here allow a more consistent correlation between tectono-volcanic Permian events along the paleo-Pacific margin of southwestern Gondwana and the geological evolution of neighboring Paleozoic foreland basins in South America and Africa. (C) 2010 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Contribution of SHRIMP U-Pb zircon geochronology to unravelling the evolution of Brazilian Neoproterozoic fold belts

The South-American continent is constituted of three major geologic-geotectonic entities the homonym platform (consolidated at the end of the Cambrian) the Andean chain (essentially Meso-Cenozoic) and the Patagonian terrains affected by tectonism and magmatism through almost all of the Phanerozoic The platform is constituted by a series of cratonic nuclei (pre-Tonian fragments of the Rodinia fission) surrounded by a complex fabric of Neoproterozoic structural provinces Two major groups of orogenic processes (plate interaction cycles) constitute the evolution of these provinces the older occurred in the Tonian (smaller in area) and the younger Brasiliano that is present in all provinces The Tonian cycles (pre-Rodinia fission?) are still being sorted out and many questions still need to be answered The Brasiliano orogenic collage events (post-Rodinia fission?) developed in three main stages in part coeval from a province to another and are 650-600 580-560 and 540-500 Ma respectively (the late event reaching the Ordovician) The first group of orogenies is recorded in practically all provinces The third group is restricted to part of the Mantiqueira Province (southeast of the platform Buzios Orogeny) and present in the Pampean province (SW of the platform) For all these groups of orogenic events there are considerable records of rock assemblages related to processes of convergent plate interaction opening accretion collision and further extrusion There is a good correlation between the geologic and geotectonic data and geochemical and isotopic data The late tectonic processes (post-orogenic magmatism foreland basins etc) of the first two groups compete in time in distinct spaces with the peak of orogenic processes in the third group The introduction of the SHRIMP U-Pb methodology was fundamental to separate the Tonian and post-Tonian orogenic groups and their respective divisions in time and space Thus there are still many open points/problems which lead to expectations of addressing these issues in the near future with the more Intense use of this methodology (C) 2010 Elsevier B V All rights reserved

Geochronological data from the Faxinal coal succession, southern Parana Basin, Brazil: A preliminary approach combining radiometric U-Pb dating and palynostratigraphy

A radiometric zircon age of 285.4 +/- 8.6 Ma (IDTIMS U-Pb) is reported from a tonstein layer interbedded with coal seams in the Faxinal coalfield, Rio Grande do Sul, Brazil. Calibration of palynostratigraphic data with the absolute age shows that the coal depositional interval in the southern Parana Basin is constrained to the Sakmarian. Consequently, the basal Gondwana sequence in the southern part of the basin should lie at the Carboniferous-Permian boundary, not within the Sakmarian as previously considered. The new results are significant for correlations between the Parana Basin and the Argentinian Paganzo Basin (302 +/- 6 Ma and 288 +/- 7 Ma) and with the Karoo Basin, specifically with the top of the Dwyka Tillite (302 +/- 3 Ma and 299.2 +/- 3.2 Ma) and the lowermost Ecca Group (288 +/- 3 Ma and 289.6 +/- 3.8 Ma). The evidence signifies widespread latest Carboniferous volcanic activity in western Gondwana. (C) 2007 Elsevier Ltd. All rights reserved.

GEOCHEMISTRY AND U-PB ZIRCON AGE OF THE INTERNAL OSSA-MORENA ZONE OPHIOLITE SEQUENCES: A REMNANT OF RHEIC OCEAN IN SW IBERIA

The Early Paleozoic geodynamic evolution in SW Iberia is believed to have been dominated by the opening of the Rheic Ocean. The Rheic Ocean is generally accepted to have resulted from the drift of peri-Gondwanan terranes such as Avalonia from the northern margin of Gondwana during Late Cambrian-Early Ordovician times. The closure of the Rheic Ocean was the final result of a continent-continent collision between Gondwana and Laurussia that produced the Variscan orogen. The Ossa-Morena Zone is a peri-Gondwana terrane, which preserves spread fragments of ophiolites - the Internal Ossa-Morena Zones Ophiolite Sequences (IOMZOS). The final patchwork of the IOMZOS shows a complete oceanic lithospheric sequence with geochemical characteristics similar to the ocean-floor basalts, without any orogenic fingerprint and/or crustal contamination. The IOMZOS were obducted and imbricated with high pressure lithologies. Based on structural, petrological and whole-rock geochemical data, the authors argue that the IOMZOS represent fragments of the oceanic lithosphere from the Rheic Ocean. Zircon SHRIMP U-Pb geochronological data on metagabbros point to an age of ca. 480 Ma for IOMZOS, providing evidence of a well-developed ocean in SW Iberia during this period, reinforcing the interpretation of the Rheic Ocean as a wide ocean among the peri-Gondwanan terranes during Early Ordovician times.

U-Pb-Hf-trace element systematics and geochronology of zircon from a granulite-facies metamorphosed mafic-ultramafic layered complex in Central Brazil

Zircon recrystallization is a common process during high-grade metamorphism and promotes partial or complete resetting of the original isotopic and chemical characteristics of the mineral and thus complicates U-Pb geochronological interpretation. In Central Brazil, this complexity may be illustrated by three composite mafic-ultramafic intrusions metamorphosed under amphibolite-to-granulite conditions. Their ages of emplacement and metamorphic ages have been a matter of controversy for the last thirty years. The Serra da Malacacheta and Barro Alto complexes make up the southernmost of these layered bodies and four samples from distinct rock types were investigated in order to verify the consequences of metamorphic alteration of zircon for U-Pb dating. Cathodoluminescent imaging reveals internal features which are typical of concomitant dissolution-reprecipitation processes, such as convolute zoning and inward-moving recrystallization fronts, even in samples in which partially preserved igneous textures are observed. Due to this extensive alteration, LA-ICPMS U-Pb isotopic analysis yielded inconclusive data. However, in situ Hf isotopic and trace-element analyses help to clarify the real meaning of the geochronological data. Low Lu/Hf (<0.004) and homogeneous (176)Hf/(177)Hf(t) values imply that the zircon populations within individual samples have crystallized in a single episode, despite the observed variations in age values. Trace element signatures of zircon grains from garnet-bearing samples reveal that they were unreactive to the development of the peak metamorphism mineral assemblage and, thus, the main chemical feature in such grains is attributed to a coupled dissolution-reprecipitation process. However, in the Cafelandia amphibolite an additional alteration process is identified, probably related to the influx of late-stage fluids. Combined isotopic and geochemical investigation on zircon grains allowed the distinction of two magmatic events. The first corresponds to the crystallization of the Serra da Malacacheta Complex and characterizes a juvenile magmatism at similar to 1.3 Ga. The younger episode, recognized in the Barro Alto Complex, is dated at ca. 800 Ma and is represented by mafic and ultramafic rocks showing intense contamination with continental crust, implying that the emplacement took place, most likely, in a continental back-arc setting. Altered zircon domains as well as titanite grains date the metamorphic event at ca. 760-750 Ma. (C) 2011 Elsevier B.V. All rights reserved.

Magnetic fabric and zircon U-Pb geochronology of the Itaoca pluton: Implications for the Brasiliano deformation of the southern Ribeira Belt (SE Brazil)

The Itaoca pluton consists of porphyritic monzogranite that intruded the upper crust into low-grade metasedimentary rocks of the Apiai Dornain (Ribeira Belt). Anisotropy of magnetic susceptibility and zircon U-Pb (Shrimp) geochronology were combined to determine pluton emplacement mechanisms and its chronology relative to the collision structures of the Paranapiacaba (Brasiliano II) orogenic system. Magnetic susceptibility ranges between 4 and 38 x 10(-3) SI, and thermomagnetic measurements indicate multidomain magnetite is the main carrier of anisotropy. The pluton shows an ""onion-skin"" structure roughly elongated to the northeast with its hinge zone including kilometer-wide roof-pendants. Magnetic lineations are variable in orientation in consistency with the dominant oblate symmetry of the magnetic fabric. A distinct NE-trending point-maxima, however, indicates the mean lineation is parallel to the stretching direction of the transpressive deformation that affected the regional host rocks. Prismatic zircon from the monzogranite, both in the core and in the finely-zoned margins, yielded an age of 623 +/- 10 Ma. These results suggest the magmatic fabric recorded the earlier strain increments of the regional shear deformation. It may correspond to the transition from continental arc to collision tectonics of the southern Ribeira Belt. (C) 2008 Elsevier Ltd. All rights reserved.

Constraining the age of the iporanga formation with SHRIMP U-Pb zircon: Implications for possible ediacaran glaciation in the Ribeira Belt, SE Brazil

The Ribeira belt in SE Brazil is a Neoproterozoic to Early Palaeozoic orogen, whose architecture and history is not yet fully understood. The depositional age of many of the sedimentary sequences in the Ribeira Belt remains unconstrained, and with debate concerning their depositional environment and tectonic setting. In this paper we present SHRIMP zircon U/Pb age constraints for one such problematic unit in the Ribeira Belt the lporanga Formation - and discuss the significance of this age with regards to the timing of Neoproterozoic glacial events in southeast Brazil. Using a felsic volcanic unit immediately under the lporanga Formation and granite cobbles from breccias in its basal parts a reconnaissance SHRIMP U/Pb zircon maximum depositional age of 580 Ma is assigned for the base of this unit. This age is marginally younger than the 625605 Ma ages for intrusions into the Lajeado and Ribeira subgroups, with which the lporanga Formation is in tectonic contact. This indicates that the Lajeado and Ribeira subgroups are not stratigraphically equivalent to the lporanga Formation, as thought previously by some workers. The maximum depositional age of 580 Ma also places a maximum time constraint on the tectonic juxtaposition of the lporanga Formation with other supracrustal units, and on the greenschist facies metamorphism and isoclinal folding that affected it. The potential glacial origin for the lporanga Formation, if correct, would place it in the late Ediacaran - provisionally equivalent to the Gaskiers glaciation. (c) 2007 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

The onset of flood basalt volcanism, Northern Parana Basin, Brazil: A precise U-Pb baddeleyite/zircon age for a Chapeco-type dacite

We report the first U-Pb baddeleyite/zircon date for a felsic volcanic rock from the Parana Large Igneous Province in south Brazil. The new date of 134.3 +/- 0.8 Ma for a hypocrystalline Chapeco-type dacite from Ourinhos (northern Parana basin) is an important regional time marker for the onset of flood basalt volcanism in the northern and western portion of the province. The dated dacite was erupted onto basement rocks and is overlain by a high-Ti basalt sequence, interpreted to be correlative with Pitanga basalts elsewhere. This new U-Pb date for the Ourinhos dacite is consistent with the local stratigraphy being slightly older than the few reliable step-heating (40)Ar/(39)Ar dates currently available for overlying high-Ti basalts (133.6-131.5 Ma). This indicates an similar to 3 Ma time span for the building of the voluminous high-Ti lava sequence of the Parana basin. On the other hand, it overlaps the (40)Ar/(39)Ar dates (134.8-134.1 Ma) available for the stratigraphically older low-Ti basalt (Gramado + Esmeralda types) and dacite-rhyolite (Palmas type) sequences from South Brazil, which is consistent with the short-lived character of this volcanism and its rapid succession by the high-Ti sequence. (C) 2010 Elsevier B.V. All rights reserved.

Nd and Pb isotope signatures on the Southeastern South American upper margin: Implications for sediment transport and source rocks

Neodymium and lead isotope values in sediment samples were used to interpret sediment transport and source rocks on the Southeastern South American upper margin. The sediments of the Argentinian margin exhibit an average epsilon(Nd) value of -1.9, indicating the influence of the Andean rocks as sediment sources. Sediments from the Rio de La Plata estuary show an average epsilon(Nd) value of -9.6 which is similar to that of the Southern Brazilian Upper Margin. Finally, sediments of Southeastern Brazil, which are associated with the transport of the Brazil Current exhibit an average epsilon(Nd) of -13.0. The Pb isotope signatures also confirm the differentiation of source rocks in the sedimentation of the study area. In addition, Pb isotopes helped to establish the extent of the influence of the Rio de La Plata on the sedimentation of the Southern Brazilian margin. In terms of Pb isotopes the sediments from the Rio de La Plata estuary and Southern Brazil are more radiogenic than those of Southeastem Brazil and the Argentinian margin. (c) 2007 Elsevier B.V. All rights reserved.

U-Pb zircon and (40)Ar-(39)Ar K-feldspar dating of syn-sedimentary volcanism of the Neoproterozoic Marica Formation: constraining the age of foreland basin inception and inversion in the Camaqua Basin of southern Brazil

New U-Pb zircon and (40)Ar-(39)Ar K-feldspar data are presented for syn-sedimentary volcanogenic rocks from the Neoproterozoic Marica Formation, located in the southern Brazilian shield. Seven (of nine) U-Pb sensitive high-resolution ion microprobe analyses of zircons from pyroclastic cobbles yield an age of 630.2 +/- 3.4 Ma (2 sigma), interpreted as the age of syn-sedimentary volcanism, and thus of the deposition itself. This result indicates that the Marica Formation was deposited during the main collisional phase (640-620 Ma) of the Brasiliano II orogenic system, probably as a forebulge or back-bulge, craton-derived foreland succession. Thus, this unit is possibly correlative of younger portions of the Porongos, Brusque, Passo Feio, Abapa (Itaiacoca) and Lavalleja (Fuente del Puma) metamorphic complexes. Well-defined, step-heating (40)Ar-(39)Ar K-feldspar plateau ages obtained from volcanogenic beds and pyroclastic cobbles of the lower and upper successions of the Marica Formation yielded 507.3 +/- 1.8 Ma and 506.7 +/- 1.4 Ma (2 sigma), respectively. These data are interpreted to reflect total isotopic resetting during deep burial and thermal effects related to magmatic events. Late Middle Cambrian cooling below ca. 200 degrees C, probably related to uplift, is tentatively associated with intraplate effects of the Rio Doce and/or Pampean orogenies (Brasiliano III system). In the southern Brazilian shield, these intraplate stresses are possibly related to the dominantly extensional opening of a rift or a pull-apart basin, where sedimentary rocks of the Camaqua Group (Santa Barbara and Guaritas Formations) accumulated.