Age and geochemistry of mantle peridotites and diorite dykes from the Baldissero body: Insights into the Paleozoic-Mesozoic evolution of the Southern Alps

Trace element and isotopic data obtained for mantle spinel Iherzolites and diorite dykes from the Baldissero massif (Ivrea-Verbano Zone, Western Italy) provide new, valuable constraints on the petrologic and geodynamic evolution of the Southern Alps in Paleozoic to Mesozoic times. Whole rock and mineral chemistry indicates that Baldissero Iherzolites can be regarded as refractory mantle residues following limited melt extraction. In particular, the Light Rare Earth Elements (LREE)-depleted and fractionated compositions of whole rock and clinopyroxene closely match modelling results for refractory residues after low degrees (similar to 4-5%) of near-fractional melting of depleted mantle, possibly under garnet-facies conditions. Following this, the peridotite sequence experienced subsolidus re-equilibration at lithospheric spinel-facies conditions and intrusion of several generations of dykes. However, Iherzolites far from dykes show very modest metasomatic changes, as evidenced by the crystallisation of accessory titanian pargasite and the occurrence of very slight enrichments in highly incompatible trace elements (e.g. Nb). The Re-Os data for Iherzolites far from the dykes yield a 376 Ma (Upper Devonian) model age that is considered to record a partial melting event related to the Variscan orogenic cycle s.l. Dioritic dykes cutting the mantle sequence have whole rock, clinopyroxene and plagioclase characterised by high radiogenic Nd and low radiogenic Sr, which point to a depleted to slightly enriched mantle source. Whole rock and mafic phases of diorites have high Mg# values that positively correlate with the incompatible trace element concentrations. The peridotite at the dyke contact is enriched in orthopyroxene, iron and incompatible trace elements with respect to the Iherzolites far from dykes. Numerical simulations indicate that the geochemical characteristics of the diorites can be explained by flow of a hydrous, silica-saturated melt accompanied by reaction with the ambient peridotite and fractional crystallisation. The composition of the more primitive melts calculated in equilibrium with the diorite minerals show tholeiitic to transitional affinity. Internal Sm-Nd, three-point isochrons obtained for two dykes suggest an Upper Triassic-Lower Jurassic emplacement age (from 204 31 to 198 29 Ma). Mesozoic igneous events are unknown in the southern Ivrea-Verbano Zone (IVZ), but the intrusion of hydrous melts, mostly silica-saturated, have been well documented in the Finero region, i.e. the northernmost part of IVZ and Triassic magmatism with calc-alkaline to shoshonitic affinity is abundant throughout the Central-Eastern Alps. The geochemical and chronological features of the Baldissero diorites shed new light on the geodynamic evolution of the Southern Alps before the opening of the Jurassic Tethys. (C) 2010 Elsevier B.V. All rights reserved.

Zr- AND Ba-RICH MINERALS FROM THE PONTE NOVA ALKALINE MAFIC-ULTRAMAFIC MASSIF, SOUTHEASTERN BRAZIL: INDICATION OF AN ENRICHED MANTLE SOURCE

Zirconium- and Ba-rich minerals are found in gabbroic rocks from the Ponte Nova alkaline mafic-ultramafic massif in southeastern Brazil. The unusual mineralogical assemblage includes zirconolite, baddeleyite, Ba-rich alkali feldspar, and Ba- and Ti-rich biotite. Zirconolite of the Ponte Nova massif has higher levels of Zr (up to 1.172 apfu) than those registered in other terrestrial rocks and a prominent enrichment in the light rare-earth elements. Baddeleyite contains small quantities of Hf, Ti, and Fe. The Ba-rich alkali feldspar and Ba- and Ti-rich biotite contain up to 9.25 and 7.35 wt% BaO, respectively, and the biotite contains up to 12.01 wt% TiO(2). In the different intrusions of the Ponte Nova massif, such an unusual assemblage typifies the residual magma after the crystallization of clinopyroxene and olivine from previously enriched basanitic parental magma. The different trends of enrichments in REE and Th + U found for zirconolite of the intrusions of the Ponte Nova massif provide a better understanding of the variable degrees of enrichment of incompatible elements of the distinct gabbroic bodies. A lithospheric mantle source enriched in incompatible elements by the metasomatic action of volatile-rich fluids and with the presence of phlogopite or amphibole (or both) and other minor accessory phases could explain the presence of the Zr- and Ba-rich minerals in this gabbroic massif.

Rhyacian (2.23-2.20 Ga) juvenile accretion in the southern Sao Francisco craton, Brazil: Geochemical and isotopic evidence from the Serrinha magmatic suite, Mineiro belt

The Serrinha magmatic suite (Mineiro belt) crops out in the southern edge of the Sao Francisco craton, comprising the Brito quartz-diorite, Brumado de Cima and Brumado de Baixo granodiorites, granophyres and felsic sub-volcanic and volcanic rocks, part of which intruded into the Nazareno greenstone belt. The suite rocks have petrographic features that are consistent with magma supercooling due to the low water content combined with volatile loss, leading to crystallization of quartz and alkaline feldspar at the rims of plagioclase phenocrysts (granophyric intergrowth). The investigated rocks are sub-alkaline, calc-alkaline and show low content in rare earth elements. The U-Pb zircon crystallization ages for the Brumado de Cima granodiorite [2227 +/- 22 (23) Ma] and a coeval granophyre [2211 +/- 22 (23) Ma], coupled with available single-zircon Pb evaporation ages for the Brito and Brumado de Baixo plutons, are significantly older than the ""Minas orogeny"" (ca. 2100-2050 Ga) of Quadrilatero Ferrifero area, eastward from the Serrinha suite. Our data establish an early Rhyacian event tectonically linked with the evolution of the Mineiro belt. The bulk Nd isotopic signature [low negative to positive epsilon(Nd(t)) values] of the Serrinha samples are consistent with the important role of Paleoproterozoic mantle components in the magma genesis. The integrated geologic, geochemical and isotopic information suggests that Paleoproterozoic evolution of the Mineiro belt initiated in a passive continental margin basin with deposition of the Minas Supergroup at ca. 2500 Ma. This stage was succeeded by outboard rupture of the oceanic lithosphere with development and coalescence of progressively younger magmatic arcs during Rhyacian time. One of the earliest arcs formed the Serrinha suite. The tectonic collage of the Serrinha and Ritapolis (2190-2120 Ma) arcs produced the NE-SW Lenheiro shear zone, resulting in mylonitization and recrystallization of both the granitoid intrusions and host rocks. As a matter of fact juxtaposition of distinct magmatic units in age and origin took place along the Lenheiros structure in this sector of the Mineiro belt. (C) 2009 Elsevier Ltd. All rights reserved.

Tectono-sedimentary evolution of the Neoproterozoic BIF-bearing Jacadigo Group, SW-Brazil

The Jacadigo Group contains one of the largest sedimentary iron and associated manganese deposits of the Neoproterozoic. Despite its great relevance, no detailed sedimentological study concerning the unit has been carried out to date. Here we present detailed sedimentological data and interpretation on depositional systems, system tracts, external controls on basin evolution, basin configuration and regional tectonic setting of the Jacadigo Basin. Six depositional systems were recognized: (I) an alluvial fan system; (II) a siliciclastic lacustrine system; (III) a fan-delta system; (IV) a bedload-dominated river system; (V) an iron formation-dominated lacustrine or marine gulf system; and (VI) a rimmed carbonate platform system. The interpreted depositional systems are related to three tectonic system tracts. The first four depositional systems are mainly made of continental siliciclastics and refer to the rift initiation to early rift climax stage; the lake/gulf system corresponds to the mid to late rift climax stage and the carbonate platform represents the immediate to late post rift stage (Bocaina Formation deposits of the Ediacaran fossil-bearing Corumba Group). The spatial distribution of the depositional systems and associated paleocurrent patterns indicate a WNW-ESE orientation of the master fault zone related to the formation of the Jacadigo Basin. Thus, the iron formations of the Jacadigo Group were deposited in a starved waterbody related to maximum fault displacement and accommodation rates in a restricted continental rift basin. The Fe-Si-Mn source was probably related to hydrothermal plume activity that reached the basin through the fault system during maximum fault displacement phases. Our results also suggest a restricted tectono-sedimentary setting for the type section of the Puga Formation. The Jacadigo Group and the Puga Formation, usually interpreted as glacial deposits, are readdressed here as basin margin gravitational deposits with no necessary relation to glacial processes. (C) 2011 Elsevier B.V. All rights reserved.

Petrology and geochemistry of the banded iron formation in the Eastern Sierras Pampeanas of San Luis (Argentina): Implications for the evolution of the Nogoli Metamorphic Complex

The metamorphosed banded iron formation from the Nogoli Metamorphic Complex of western Sierra de San Luis, Eastern Sierras Pampeanas of Argentina (Nogoli area, 32 degrees 55`S-66 degrees 15`W) is classified as an oxide facies iron formation of Algoma Type, with a tectonic setting possibly associated with an island arc or back arc, on the basis of field mapping, mineral and textural arrangements and whole rock geochemical features. The origin of banded iron formation is mainly related to chemical precipitation of hydrogenous sediments from seawater in oceanic environments. The primary chemical precipitate is a result of solutions that represent mixtures of seawater and hydrothermal fluids, with significant dilution by maficultramafic volcanic and siliciclastic materials. Multi-stage T(DM) model ages of 1670, 1854 and 1939 Ma and positive, mantle-like xi Nd((1502)) values of +3.8, +1.5 and +0.5 from the banded iron formation are around the range of those mafic to ultramafic meta-volcanic rocks of Nogoli Metamorphic Complex, which are between 1679 and 1765 Ma and +2.64 and +3.68, respectively. This Sm and Nd isotopic connection suggests a close genetic relationship between ferruginous and mafic-ultramafic meta-volcanic rocks, as part of the same island arc or back arc setting. A previous Sm-Nd whole rock isochron of similar to 1.5 Ga performed on mafic-ultramafic meta-volcanic rocks led to the interpretation that chemical sedimentation as old as Mesoproterozoic is possible for the banded iron formation. A clockwise P-T path can be inferred for the regional metamorphic evolution of the banded iron formation, with three distinctive trajectories: (1) Relict prograde M(1)-M(3) segment with gradual P and T increase from greenschist facies at M(1) to amphibolite facies at M(3). (2) Peak P-T conditions at high amphibolite-low granulite facies during M(4). (3) Retrograde counterpart of M(4), that returns from amphibolite facies and stabilizes at greenschist facies during M(5). Each trajectory may be regarded as produced by different tectonic events related to the Pampean? (1) and the Famatinian (2 and 3) orogenies, during the Early to Middle Paleozoic. The Nogoli Metamorphic Complex is interpreted as part of a greenstone belt within the large Meso- to Neoproterozoic Pampean Terrane of the Eastern Sierras Pampeanas of Argentina. (C) 2009 Elsevier Ltd. All rights reserved.

Estudo dos óxidos A2B2O7 e ABO3 a base de terras raras, para aplicações térmicas e catalíticas a altas temperaturas

Rare earth elements have recently been involved in a range of advanced technologies like microelectronics, membranes for catalytic conversion and applications in gas sensors. In the family of rare earth elements like cerium can play a key role in such industrial applications. However, the high cost of these materials and the control and efficiencies associated processes required for its use in advanced technologies, are a permanent obstacle to its industrial development. In present study was proposed the creation of phases based on rare earth elements that can be used because of its thermal behavior, ionic conduction and catalytic properties. This way were studied two types of structure (ABO3 and A2B2O7), the basis of rare earths, observing their transport properties of ionic and electronic, as well as their catalytic applications in the treatment of methane. For the process of obtaining the first structure, a new synthesis method based on the use of EDTA citrate mixture was used to develop a precursor, which undergone heat treatment at 950 ° C resulted in the development of submicron phase BaCeO3 powders. The catalytic activity of perovskite begins at 450 ° C to achieve complete conversion at 675 ° C, where at this temperature, the catalytic efficiency of the phase is maximum. The evolution of conductivity with temperature for the perovskite phase revealed a series of electrical changes strongly correlated with structural transitions known in the literature. Finally, we can establish a real correlation between the high catalytic activity observed around the temperature of 650 ° C and increasing the oxygen ionic conductivity. For the second structure, showed clearly that it is possible, through chemical processes optimized to separate the rare earth elements and synthesize a pyrochlore phase TR2Ce2O7 particular formula. This "extracted phase" can be obtained directly at low cost, based on complex systems made of natural minerals and tailings, such as monazite. Moreover, this method is applied to matters of "no cost", which is the case of waste, making a preparation method of phases useful for high technology applications

Petrologia do plúton Serra da Macambira, neoproterozóico da faixa seridó, província Borborema (NE do Brasil)

The final stage of Brasiliano/Pan-African orogeny in the Borborema Province is marked by widespread plutonic magmatism. The Serra da Macambira Pluton is an example of such plutonism in Seridó Belt, northeastern Borborema Province, and it is here subject of geological, petrographic, textural, geochemical and petrogenetic studies. The pluton is located in the State of Rio Grande do Norte, intrusive into Paleoproterozoic orthogneisses of the Caicó Complex and Neoproterozoic metassupracrustal rocks of the Seridó Group. Based upon intrusion/inclusion field relationships, mineralogy and texture, the rocks are classified as follows: intermediate enclaves (quartz-bearing monzonite and biotite-bearing tonalite), porphyritic monzogranite, equigranular syenogranite to monzogranite, and late granite and pegmatite dykes. Porphyritic granites and quartz-bearing monzonites represent mingling formed by the injection of an intermediate magma into a granitic one, which had already started crystallization. Both rocks are slightly older than the equigranular granites. Quartz-bearing monzonite has K-feldspar, plagioclase, biotite, hornblende and few quartz, meanwhile biotite-bearing tonalite are rich in quartz, poor in K-feldspar and hornblende is absent. Porphyritic and equigranular granites display mainly biotite and rare hornblende, myrmekite and pertitic textures, and zoned plagioclase pointing out to the relevance of fractional crystallization during magma evolution. Such granites have Rare Earth Elements (REE) pattern with negative Eu anomaly and light REE enrichment when compared to heavy REE. They are slight metaluminous to slight peraluminous, following a high-K calc-alkaline path. Petrogenesis started with 27,5% partial melting of Paleoproterozoic continental crust, generating an acid hydrous liquid, leaving a granulitic residue with orthopyroxene, plagioclase (An40-50), K-feldspar, quartz, epidote, magnetite, ilmenite, apatite and zircon. The liquid evolved mainly by fractional crystallization (10-25%) of plagioclase (An20), biotite and hornblende during the first stages of magmatic evolution. Granitic dykes are hololeucocratic with granophyric texture, indicating hypabissal crystallization and REE patterns similar to A-Type granites. Preserved igneous textures, absence or weak imprint of ductile tectonics, association with mafic to intermediate enclaves and alignment of samples according to monzonitic (high-K calcalkaline) series all indicate post-collisional to post-orogenic complexes as described in the literature. Such interpretation is supported by trace element discrimination diagrams that place the Serra da Macambira pluton as late-orogenic, probably reflecting the vanishing stages of the exhumation and collapse of the Brasiliano/Pan-African orogen.

Phosphate functionalization of spongiolite surface

Spongiolite from Mato Grosso do Sul (Brazil), natural inorganic composite constituted of silica needles, was treated with concentrated phosphoric acid at high temperatures. Superficial coating of the needles was proved to be constituted of silicon diphosphate, a compound offering six-coordinated silicon sites. Owing to the affinity of three charged ions to phosphate groups, this coating acts as specific adsorbent for the rare earth elements which prefer octahedral coordination (starting from samarium, yttrium included). The uptake of lanthanum and neodymium are significantly lower due to different coordination tendencies. Lanthanide fixation upon silica with PO4 groups anchored on its surface may be useful in the manufacturing of special phosphate-silicate glasses. (C) 2003 Elsevier B.V. All rights reserved.

Sm-Nd system in total rock open versus closed isotopic composition in zones of high deformation

High strain shear zones of Brasiliano age, developed in Paleoproterozoic basement gneiss of the Caicó region, Borborema Province, NE Brazil, were associated with medium- to low-grade metamorphism and deformational processes that transformed porphyritic augen gneiss into muscovite quartzite, modifying their original mineralogy and chemical properties. During the last hydrothermal event mobility of major, minor and trace elements was great, whereas the pattern of Rare Earth Elements was not changed. We carried out a Sm-Nd isotopic study in these rocks in order to understand the behavior of Nd isotopes during mylonite generation. TDM model ages at around 2.6 Ga and εNd (t) values for both protolith and transformed rock suggest that the Nd isotopic system remained closed, recording the original source rock signature, despite undergoing two superposed metamorphic events. These new Sm-Nd results provide important information on the geologic evolution of basement rocks in the central Rio Grande do Norte Terrane of the Borborema Province, NE Brazil.

Red, green, and blue upconversion luminescence in ytterbium-sensitized praseodymium-doped lead-cadmium-germanate glass

Blue, green, red, and near-infrared upconversion luminescence in the wavelength region of 480 - 740 nm in Pr3+/Yb3+-codoped lead-cadmium-germanate glass under 980 nm diode laser excitation, is presented. Upconversion emission peaks around 485, 530, 610, 645, and 725 nm which were ascribed to the 3P0 - 3HJ (J=4, 5, and 6), and 3P0 - 3FJ (J=2, and 3,4), transitions, respectively, were observed. The population of the praseodymium upper 3P0 emitting level was accomplished through a combination of ground-state absorption of Yb3+ ions at the 2F7/2, energy-transfer Yb3+(2F 5/2) Pr3+(3H4), and excited-state absorption of Pr3+ ions provoking the 1G4 - 3P0 transition. The dependence of the upconversion luminescence upon the Yb3+-concentration and diode laser power, is also examined, in order to subsidize the proposed upconversion excitation mechanism.

Thermal studies of solid 2-methoxybenzylidenepyruvate of lighter trivalent lanthanides

Solid-state compounds with a general formula of LnL3· nH2O, where Ln stands for lighter trivalent lanthanides (lanthanum to samarium), L is 2-methoxybenzylidenepyruvate and n=1.5, 2, 2, 1.5 and 2, respectively, have been synthesized. On heating these compounds are decompose in two or three steps. They lose their hydration water in the first step and the thermal decomposition of the anhydrous compounds occurs with the formation of the respective oxide, CeO2, Pr6O11 and Ln 2O3 (Ln=La, Nd, Sm) as final residue. The dehydration enthalpies found for these compounds (La to Sm) were: 222.7, 163.6, 497.7, 513.9 and 715.4 kJ mol-1, respectively. © 2005 Akadémiai Kiadó, Budapest.

Thermal studies on solid 2-chlorobenzylidenepyruvate of lighter trivalent lanthanides

Solid compounds of general formula LnL3 for La and Ce and LnL3·nH2O for Pr, Nd and Sm where Ln stands for trivalent lanthanides, L is 2-chlorobenzylidenepyruvate and n=2, 3 and 2 respectively, have been synthesized. On heating these compounds decompose in two or five steps. They lose the hydration water in the first step and the thermal decomposition of the anhydrous compounds occurs with the formation of the respective oxide, CeO2, Pr6O11 and Ln 2O3 (Ln=La, Nd, Sm) as final residue. The dehydration enthalpies found for these compounds (Pr, Nd and Sm) were: 140.1, 148.2 and 221.3 kJ mol-1, respectively. © 2005 Akadémiai Kiadó, Budapest.

Synthesis, characterization and thermal behavior of solid state compounds of heavy trivalent lanthanide succinates

Solid-state Ln-L compounds, where Ln stands for heavy trivalent lanthanides or yttrium(III) (Tb-Lu, Y) and L is succinate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy, TG-DTA coupled to FTIR, elemental analysis, X-ray powder diffractometry and complexometry were used to characterize and study the thermal behavior of these compounds. For the terbium to thulium and yttrium compounds, the dehydration, as well the thermal decomposition of the anhydrous compound occurs in two consecutive steps, while ytterbium and lutetium the dehydration occurs in a single step. The results also led to information about the ligand's denticity, thermal stability and thermal decomposition of these compounds. © 2013 Elsevier B.V.

Thermoanalytical study of heavier trivalent lanthanides fumarates

Solid-state heavier lanthanides fumarates compounds have been synthesized, and the compounds were characterized by employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), TG coupled to FTIR, elemental analysis, and complexometry. On heating, the dehydration occurs in a single and two consecutive steps and the thermal decomposition of the anhydrous compounds occurs in consecutive and/or overlapping steps, with formation of the respective oxides: Tb4O7 and Ln2O3 (Ln=Dy to Lu). The results also led to information about composition, thermal behavior, and the type of coordination of the isolated compounds. © 2012 Akadémiai Kiadó, Budapest, Hungary.

Caracterização dos diamantes da província kimberlítica de Juína (MT), e distritos diamantíferos de Espigão D'Oeste (RO), Cacoal (RO) e Diamantina (MG)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)