980 resultados para Pb-isotope
Resumo:
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.
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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.
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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.
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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.
Resumo:
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
Resumo:
The lavas produced by the Timanfaya eruption of 1730-1736 (Lanzarote, Canary Islands) contain a great many sedimentary and metamorphic (metasedimentary), and mafic and ultramafic plutonic xenoliths. Among the metamorphosed carbonate rocks (calc-silicate rocks [CSRs]) are monomineral rocks with forsterite or wollastonite, as well as rocks containing olivine +/- orthopyroxene +/- clinopyroxene +/- plagioclase: their mineralogical compositions are identical to those of the mafic (gabbros) and ultramafic (dunite, wherlite and lherzolite) xenoliths. The (87)Sr/(16)Sr (around 0.703) and (143)Nd/(144)Nd (around 0.512) isotope ratios of the ultramafic and metasedimentary xenoliths are similar, while the (147)Sm/(144)Nd ratios show crustal values (0.13-0.16) in the ultramafic xenoliths and mantle values (0.18-0.25) in some CSRs. The apparent isotopic anomaly of the metamorphic xenoliths can be explained in terms of the heat source (basaltic intrusion) inducing strong isotopic exchange ((87)Sr/(86)Sr and (143)Nd/(144)Nd) between metasedimentary and basaltic rocks. Petrofabric analysis also showed a possible relationship between the ultramafic and metamorphic xenoliths. (C) 2009 Elsevier B.V. All rights reserved.
Resumo:
The basement in the `Altiplano` high plateau of the Andes of northern Chile mostly consists of late Paleozoic to Early Triassic felsic igneous rocks (Collahuasi Group) that were emplaced and extruded along the western margin of the Gondwana supercontinent. This igneous Suite crops out in the Collalluasi area and forms the backbone of most of the high Andes from latitude 20 degrees to 22 degrees S. Rocks of the Collahuasi Group and correlative formations form art extensive belt of volcanic and subvolcanic rocks throughout the main Andes of Chile, the Frontal Cordillera of Argentina (Choiyoi Group or Choiyoi Granite-Rhyolite Province), and the Eastern Cordillera of Peru. Thirteen new SHRIMP U-Pb zircon ages from the Collahuasi area document a bimodal timing for magnatism, with a dominant peak at about 300 Ma and a less significant one at 244 Ma. Copper-Mo porphyry mineralization is related to the younger igneous event. Initial Hf isotopic ratios for the similar to 300 Ma zircons range from about -2 to +6 indicating that the magmas incorporated components with a significant crustal residence time. The 244 Ma magmas were derived from a less enriched source, with the initial HT values ranging from +2 to +6, suggestive of a mixture with a more depleted component. Limited whole rock (144)Nd/(143)Nd and (87)Sr/(86)Sr isotopic ratios further support the likelihood that the Collahuasi Group magmatism incorporated significant older crustal components, or at least a mixture of crustal sources with more and less evolved isotopic signatures. (C) 2007 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.
Resumo:
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.
Resumo:
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.
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One of the main questions on Neoproterozoic geology regards the extent and dynamics of the glacial systems that are recorded in all continents. We present evidence for short transport distances and localized sediment sources for the Bebedouro Formation, which records Neoproterozoic glaciomarine sedimentation in the central-eastern Sao Francisco Craton (SFC), Brazil. New data are presented on clast composition, based on point counting in thin section and SHRIMP dating of pebbles and detrital zircon. Cluster analysis of clast compositional data revealed a pronounced spatial variability of clast composition on diamictite indicating the presence of individual glaciers or ice streams feeding the basin. Detrital zircon ages reveal distinct populations of Archean and Palaeoproterozoic age. The youngest detrital zircon dated at 874 +/- 9 Ma constrains the maximum depositional age of these diamictites. We interpret the provenance of the glacial diamictites to be restricted to sources inside the SFC, suggesting deposition in an environment similar to ice streams from modern, high latitude glaciers.
Resumo:
Important concentrations of tourmaline occur as gold-bearing stratiform tourmalinites and in mineralized quartz-tourmaline veins at the Tapera Grande and Quartzito gold prospects in the Mesoproterozoic Serra do Itaberaba Group, central Ribeira Belt (Sao Paulo State, SE Brazil). The main rock types in both prospects constitute the volcanic-sedimentary Morro da Pedra Preta Formation, which formed in a submarine back-arc setting. At Tapera Grande, the volcanic-sedimentary sequence is composed of metabasic and metavolcaniclastic rocks, graphitic and sulfur-rich metapelites, banded iron formation, metandesite, metarhyolite, calcsilicates, tourmalinites and metahydrothermalites derived from mafic and felsic rocks. The Mesoproterozoic rocks at Quartzito prospect are lithologically similar but they have been affected by Neoproterozoic faulting and shearing and by the emplacement of granitic rocks, resulting in the formation of tourmaline-rich quartz-carbonate veins with gold and base metal mineralization. We conducted a chemical and B-isotope study of tourmalines in order to better understand the origin of the stratiform tourmalinites in the Morro da Pedra Preta Formation and their relationship with gold mineralization. The overall range of delta(11)B values obtained for the tourmalinite and vein tourmalines is between - 15%. and -5 parts per thousand, with the tourmalinites failing at the low end of this range (-15 to -8 parts per thousand). Such values are typical for continental crust and inconsistent with a primary marine boron signature as expected from the submarine-exhalative model for the gold prospects. We conclude from this that tourmaline formed or recrystallized from crustal fluids related to the amphibolite-grade metamorphism which affected the Serra do Itaberaba Group and that gold deposition occurred syn- to post-peak metamorphism by phase immiscibility, as attested by fluid inclusions in Tapera Grande tourmalinite tourmaline and quartz. The vein-hosted tourmalines at Quartzito have isotopically variable boron signatures, with heavier delta(11)B values of -5 parts per thousand to -8 parts per thousand for acicular green tourmalines and lighter values (-15 parts per thousand to -7 parts per thousand for light blue, Ti-firee tourmaline from quartz-carbonate veins). We attribute the heavier boron to fluids derived from the volcano-sedimentary rocks of marine affinity whereas the lighter boron was contributed by crustal fluids related to the granitoids or metasediments in the continental crust. (c) 2009 Elsevier B.V. All rights reserved.
Resumo:
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.
Resumo:
We developed an analytical method and constrained procedural boundary conditions that enable accurate and precise Zn isotope ratio measurements in urban aerosols. We also demonstrate the potential of this new isotope system for air pollutant source tracing. The procedural blank is around 5 ng and significantly lower than published methods due to a tailored ion chromatographic separation. Accurate mass bias correction using external correction with Cu is limited to Zn sample content of approximately 50 ng due to the combined effect of blank contribution of Cu and Zn from the ion exchange procedure and the need to maintain a Cu/Zn ratio of approximately 1. Mass bias is corrected for by applying the common analyte internal standardization method approach. Comparison with other mass bias correction methods demonstrates the accuracy of the method. The average precision of delta(66)Zn determinations in aerosols is around 0.05% per atomic mass unit. The method was tested on aerosols collected in Sin Paulo City, Brazil. The measurements reveal significant variations in delta(66)Zn(Imperial) ranging between -0.96 and -0.37% in coarse and between -1.04 and 0.02% in fine particular matter. This variability suggests that Zn isotopic compositions distinguish atmospheric sources. The isotopic light signature suggests traffic as the main source. We present further delta(66)Zn(Imperial) data for the standard reference material NIST SRM 2783 (delta 66Z(Imperial) = 0.26 +/- 0.10%).
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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.
Resumo:
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.