Sílica mesoporosa como suporte sólido para o ancoramento da molécula 4-amino-3-hidrazino-5-mercapto-1,2,4-triazole e aplicação na adsorção de Cu(II), Cd(II), Ni(II), Pb(II) e Co(II) em amostras aquosas

Pós-graduação em Química - IQ

Geoquímica e geocronologia U-Pb e ­Sm-Nd dos ortognaisses da região de Pontalina (GO), Brasil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Aprimoramento da sistemática U-Pb através do método de traços de fissão e técnicas de caracterização: termocronologia da faixa Brasília e sua correlação com a bacia do Paraná

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Discrimination of production environments of specialty coffees by means of stable isotopes and discriminant model

The south of Minas Gerais, Brazil stands out among various regions through its capacity for production of specialty coffees. Its potential, manifested through being one of the most award-winning Brazilian regions in recent years, has been recognized by the Cup of Excellence (COE). With the evident relationship between product quality and the environment in mind, the need arises for scientific studies to provide a foundation for discrimination of product origin, creating new methods for combating possible fraud. The aim of this study was to evaluate the use of carbon and nitrogen isotopes in discrimination of production environments of specialty coffees from the Serra da Mantiqueira of Minas Gerais by means of the discriminant model. Coffee samples were composed of ripe yellow and red fruits collected manually at altitudes below 1,000 m, from 1,000 to 1,200 m and above 1,200 m. The yellow and red fruits were subjected to dry processing and wet processing, with five replications. A total of 119 samples were used for discrimination of specialty coffee production environments by means of stable isotopes and statistical modeling. The model generated had an accuracy rate of 89% in discrimination of environments and was composed of the isotope variables of δ15N, δ13C, %C, %N, δD, δ18O (meteoric water) and sensory analysis scores. In addition, for the first time, discrimination of environments on a local geographic scale, within a single municipality, was proposed and successfully concluded. This shows that isotope analysis is an effective method in verifying geographic origin for specialty coffees.

Ecology, stable isotopes, and management of grassland songbirds at National Park Service properties on the Great Plains

Grassland ecosystems have been severely reduced and grassland bird populations have experienced consistent declines. National Park Service (NPS) properties on the Great Plains provide breeding habitat for grassland songbirds, though little is known about the quality of this habitat. A short-term study on songbirds at three NPS properties complemented current monitoring, providing an among park comparison addressing grassland bird productivity and fidelity relative to NPS property size. During 2008-2009, I assessed avian species richness, and estimated bird density and grassland songbird nest success. Bird species richness was greatest at small and medium sites, while number of nesting obligate species was greatest at the large site. Species-specific densities varied among sites, with few grassland obligates occurring at all three sites. Nest success estimates for grassland obligates were highest at the small site and lower at the large site. Another method to quantify habitat quality is assessment of breeding site fidelity. Current extrinsic markers used in monitoring site fidelity are inadequate for small birds; stable isotope analyses provide an alternative. I compared two techniques for assigning stable isotope tissue origin and measured grassland songbird site fidelity. My method of assigning origin provided site-specific variances of expected stable isotope values, an improvement over the most commonly used method. Fidelity tended to be higher at the large site, which may indicate a more robust breeding community of grassland birds. The small size of two of my sites precluded large sample sizes and made strong inferences difficult. To quantify how scientists cope with weak inference, I conducted a literature review. Strong inference was rarely observed, and most authors of weak-inference papers provided specific management recommendations. I suggest that adaptive management is an ideal method to resolve uncertainty from weak inference. Managers should consider my results within the context of regional and global management and the extent to which their unit might aide songbird conservation.

Temporal and Spatial Variations of Ions, Isotopes and Agricultural Contaminants in Surface Waters and Groundwater of Nebraska's Rainwater Basin Wetland Region

The wetlands of south-central Nebraska’s Rainwater Basin region are considered of international importance as a habitat for millions of migratory birds, but are being endangered by agricultural practices. The Rainwater Basin extends across 17 counties and covers 4,000 square miles. The purpose of this study was to assemble baseline chemical data for several representative wetlands across the Rainwater Basin region, and determine the use of these chemical data for investigating groundwater recharge. Eight representative wetlands were chosen across the Rainwater Basin to monitor surface and groundwater chemistry. At each site, a shallow well and deep well were installed and sampled once in the summer of 2009 and again in the spring of 2010. Wetland surface water was sampled monthly from April, 2009 to May, 2010. Waters were analyzed for major ions, nutrients, pesticides and oxygen-18 and deuterium isotopes at the University of Nebraska Water Sciences Laboratory. Geochemical analysis of surface waters presents a range of temporal and spatial variations. Wetlands had variable water volumes, isotopic compositions, ion chemistries and agricultural contaminant levels throughout the year and, except for a few trends, theses variations cannot be predicted with certainty year-to-year or wetland-to-wetland. Isotopic compositions showed evaporation was a contributor to water loss, and thus, did impact water chemistry. Surface water nitrate concentrations ranged from <0.10 to 4.04 mg/L. The nitrate levels are much higher in the groundwater, ranging from <0.10 to 18.4 mg/L, and are of concern because they are found above the maximum contaminant level (MCL) of 10 mg/L. Atrazine concentrations in surface waters ranged from <0.05 to 10.3 ppb. Groundwater atrazine concentrations ranged from <0.05 to 0.28 ppb. The high atrazine concentrations in surface waters are of concern as they are above the MCL of 3 ppb, and the highest levels occur during the spring bird migration. Most sampled groundwaters had detectable tritium indicating a mix of modern (<5 to 10 years old) and submodern (older than 1950s) recharge. The groundwater also had differences in chemical and isotope composition, and in some cases, increased nitrate concentrations, between the two sampling periods. Modern groundwater tritium ages and changes in groundwater chemical and isotopic compositions may indicate connections with surface waters in the Rainwater Basin.

Local structure around Fe ions on multiferroic Pb(Fe1/2Nb1/2)O-3 ceramics probed by x-ray absorption spectroscopy

Local structure around Fe ions on Pb(Fe1/2Nb1/2)O-3 ceramics was probed by x-ray absorption spectroscopy in order to settle the controversies about its structure. It is observed that the shell structure around Fe atoms exhibits a monoclinic local symmetry at 130 and 230 K, tetragonal local symmetry at room temperature, and cubic local symmetry at 410 K. Independently of the coordination, temperature, or symmetry, Fe-O mean bond-length does not vary significantly. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4709490]

Effects of catalyst load in Pt and Pb-based catalysts using formic acid oxidation as a model

In this paper, we discuss the effects of catalyst load with respect to carbon powder for several Pt and Pb-based catalysts, using formic acid as a model molecule. The discussion is based on electrochemical tests, a complete morphological investigation and theoretical calculations. We show that the Pt and Pb-based catalysts presented activity in formic acid oxidation at very low catalyst loads (e.g., 0.5% in respect to the carbon content). Physical characterisations demonstrate that the electrodes are composed of separated phases of Pt and lead distributed in Pt nanometric-sized islands that are heterogeneously dispersed on the carbon support and Pb ultra-small particles homogeneously distributed throughout the entire carbon surface, as demonstrated by the microscopy studies. At high catalyst loads, very large clusters of Pb(x)O(y) could be observed. Electrochemical tests indicated an increase in the apparent resistance of the system (by a factor of 19.7 Omega) when the catalyst load was increased. The effect of lead in the materials was also studied by theoretical calculations (OFT). The main conclusion is that the presence of Pb atoms in the catalyst can improve the adsorption of formic acid in the catalytic system compared with a pure Pt-based catalyst. (C) 2011 Elsevier B.V. All rights reserved.

Paper-based diffusive gradients in thin films technique coupled to energy dispersive X-ray fluorescence spectrometry for the determination of labile Mn, Co, Ni, Cu, Zn and Pb in river water

The diffusive gradients in thin films (DGT) technique has shown enormous potential for labile metal monitoring in fresh water due to the preconcentration, time-integrated, matrix interference removal and speciation analytical features. In this work, the coupling of energy dispersive X-ray fluorescence (EDXRF) with paper-based DGT devices was evaluated for the direct determination of Mn, Co. Ni, Cu, Zn and Pb in fresh water. The DGT samplers were assembled with cellulose (Whatman 3 MM chromatography paper) as the diffusion layer and a cellulose phosphate ion exchange membrane (Whatman P 81 paper) as the binding agent. The diffusion coefficients of the analytes on 3 MM chromatography paper were calculated by deploying the DGT samplers in synthetic solutions containing 500 mu g L-1 of Mn. Co, Ni, Cu, Zn and Pb (4 L at pH 5.5 and ionic strength at 0.05 mol L-1). After retrieval, the DGT units were disassembled and the P81 papers were dried and analysed by EDXRF directly. The 3 MM chromatographic paper diffusion coefficients of the analytes ranged from 1.67 to 1.87 x 10(-6) cm(2) s(-1). The metal retention and phosphate group homogeneities on the P81 membrane was studied by a spot analysis with a diameter of 1 mm. The proposed approach (DGT-EDXRF coupling) was applied to determine the analytes at five sampling sites (48 h in situ deployment) on the Piracicaba river basin, and the results (labile fraction) were compared with 0.45 mu m dissolved fractions determined by synchrotron radiation-excited total reflection X-ray fluorescence (SR-TXRF). The limits of detection of DGT-EDXRF coupling for the analytes (from 7.5 to 26 mu g L-1) were similar to those obtained by the sensitive SR-TXRF technique (3.8 to 9.1 mu g L-1). (C) 2012 Elsevier B.V. All rights reserved.

Geochemistry and Pb-207/Pb-206 zircon ages of granitoids from the southern portion of the Tamboril-Santa Quiteria granitic-migmatitic complex, Ceara Central Domain, Borborema Province (NE Brazil)

The Tamboril-Santa Quiteria Complex is an important Neoproterozoic granitic-migmatitic unit from the Ceara Central Domain that developed from ca. 650 to 610 Ma. In general the granitoids range in composition from diorite to granite with predominance (up to 85%) of granitic to monzogranitic composition with biotite as the main mafic AFM phase. Geochemical and Pb-207/Pb-206 evaporation zircon geochronology studies were applied in a group of these abundant monzogranitic rocks from the region of Novo Oriente in the southern portion of the Ceara Central Domain. In this area the granitoids are weakly peraluminous biotite granitoids and deformed biotite granitoids of high-K calc-alkaline and ferroan composition, which we interpreted as primary magmas (segregated diatexites) derived from the partial melting of crustal material. The close temporal relation of this magmatism with local eclogitic and regional high temperature metamorphism in Ceara Central Domain point out to an orogenic setting, arguably emplaced during the collisional stage. Subordinate coeval juvenile mantle incursions are also present. This crustally derived magmatism is the primary product of the continental thickening that resulted from the collision between the rocks represented by the Amazonian-West African craton (Sao Luiz cratonic fragment) to the northwest and the Paleoproterozoic-Archean basement of the Borborema Province to the southeast along the Transbrasiliano tectonic corridor. (C) 2011 Elsevier Ltd. All rights reserved.

Stable water isotopes of precipitation and firn cores from the northern Antarctic Peninsula region as a proxy for climate reconstruction

In order to investigate the climate variability in the northern Antarctic Peninsula region, this paper focuses on the relationship between stable isotope content of precipitation and firn, and main meteorological variables (air temperature, relative humidity, sea surface temperature, and sea ice extent). Between 2008 and 2010, we collected precipitation samples and retrieved firn cores from several key sites in this region. We conclude that the deuterium excess oscillation represents a robust indicator of the meteorological variability on a seasonal to sub-seasonal scale. Low absolute deuterium excess values and the synchronous variation of both deuterium excess and air temperature imply that the evaporation of moisture occurs in the adjacent Southern Ocean. The delta O-18-air temperature relationship is complicated and significant only at a (multi)seasonal scale. Backward trajectory calculations show that air-parcels arriving at the region during precipitation events predominantly originate at the South Pacific Ocean and Bellingshausen Sea. These investigations will be used as a calibration for ongoing and future research in the area, suggesting that appropriate locations for future ice core research are located above 600 m a.s.l. We selected the Plateau Laclavere, Antarctic Peninsula as the most promising site for a deeper drilling campaign.

Geochronological constraints on the age of a Permo-Triassic impact event: U-Pb and Ar-40/Ar-39 results for the 40 km Araguainha structure of central Brazil

Impact cratering has been a fundamental geological process in Earth history with major ramifications for the biosphere. The complexity of shocked and melted rocks within impact structures presents difficulties for accurate and precise radiogenic isotope age determination, hampering the assessment of the effects of an individual event in the geological record. We demonstrate the utility of a multi-chronometer approach in our study of samples from the 40 km diameter Araguainha impact structure of central Brazil. Samples of uplifted basement granite display abundant evidence of shock deformation, but U/Pb ages of shocked zircons and the Ar-40/Ar-39 ages of feldspar from the granite largely preserve the igneous crystallization and cooling history. Mixed results are obtained from in situ Ar-40/Ar-39 spot analyses of shocked igneous biotites in the granite, with deformation along kink-bands resulting in highly localized, partial resetting in these grains. Likewise, spot analyses of perlitic glass from pseudotachylitic breccia samples reflect a combination of argon inheritance from wall rock material, the age of the glass itself, and post-impact devitrification. The timing of crater formation is better assessed using samples of impact-generated melt rock where isotopic resetting is associated with textural evidence of melting and in situ crystallization. Granular aggregates of neocrystallized zircon form a cluster of ten U-Pb ages that yield a "Concordia" age of 247.8 +/- 3.8 Ma. The possibility of Pb loss from this population suggests that this is a minimum age for the impact event. The best evidence for the age of the impact comes from the U-Th-Pb dating of neocrystallized monazite and Ar-40/Ar-39 step heating of three separate populations of post-impact, inclusion-rich quartz grains that are derived from the infill of miarolitic cavities. The Pb-206/U-238 age of 254.5 +/- 3.2 Ma (2 sigma error) and Pb-208/Th-232 age of 255.2 +/- 4.8 Ma (2 sigma error) of monazite, together with the inverse, 18 point isochron age of 254 +/- 10 Ma (MSWD = 0.52) for the inclusion-rich quartz grains yield a weighted mean age of 254.7 +/- 2.5 Ma (0.99%, 2 sigma error) for the impact event. The age of the Araguainha crater overlaps with the timing of the Permo-Triassic boundary, within error, but the calculated energy released by the Araguainha impact is insufficient to be a direct cause of the global mass extinction. However, the regional effects of the Araguainha impact event in the Parana-Karoo Basin may have been substantial. (C) 2012 Elsevier Ltd. All rights reserved.

Discovery and cross-section measurement of neutron-rich isotopes in the element range from neodymium to platinum with the FRS

Using the high-resolution performance of the fragment separator FRS at GSI we have discovered 60 new neutron-rich isotopes in the atomic number range of 60 <= Z <= 78. The new isotopes were unambiguously identified in reactions with a U-238 beam impinging on a Be target at 1 GeV/nucleon. The production cross-section for the new isotopes have been measured down to the pico-barn level and compared with predictions of different model calculations. For elements above hafnium fragmentation is the dominant reaction mechanism which creates the new isotopes, whereas fission plays a dominant role for the production of the new isotopes up to thulium. (C) 2012 Elsevier B.V. All rights reserved.

Petrogenesis of syntectonic granites emplaced at the transition from thrusting to transcurrent tectonics in post-collisional setting: Whole-rock and Sr-Nd-Pb isotope geochemistry in the Neoproterozoic Quatro Ilhas and Mariscal Granites, Southern Brazil

The Neoproterozoic post-collisional period in southern Brazil (650-580 Ma) is characterized by substantial volumes of magma emplaced along the active shear zones that compose the Southern Brazilian Shear Belt. The early-phase syntectonic magmatism (630-610 Ma) is represented by the porphyritic, high-K, metaluminous to peraluminous Quatro Ilhas Granitoids and the younger heterogranular, slightly peraluminous Mariscal Granite. Quatro II has Granitoids include three main petrographic varieties (muscovite-biotite granodiorite mbg; biotite monzogranite - bmz: and leucogranite - lcg) that, although sharing some significant geochemical characteristics, are not strictly comagmatic, as shown by chemical and Sr-Nd-Pb isotope data. The most primitive muscovite-biotite granodiorite was produced by contamination of more mafic melts (possibly with some mantle component) with peraluminous crustal melts; the biotite monzogranite, although more felsic, has higher Ca, MgO,TiO2 and Ba, and lower K2O, FeOt, Sr and Rb contents, possibly reflecting some mixing with coeval mafic magmas of tholeiitic affinity; the leucogranite may be derived from pure crustal melts. The Mariscal Granite is formed by two main granite types which occur intimately associated in the same pluton, one with higher K (5-6.5 wt.% K2O) high Rb and lower CaO, Na2O, Ba and Zr as compared to the other (3-5 wt.% of K2O). The two Mariscal Granite varieties have compositional correspondence with fine-grained granites (fgg) that occur as tabular bodies which intruded the Quatro Ilhas Granoitoids before they were fully crystallized, and are inferred to correspond to the Mariscal Granite feeders, an interpretation that is reinforced by similar U-Pb zircon crystallization ages. The initial evolution of the post-collisional magmatism, marked by the emplacement of the Quatro Ilhas Granitoids varieties, activated sources that produced mantle and crustal magmas whose emplacement was controlled both by flat-lying and transcurrent structures. The transition from thrust to transcurrent-related tectonics coincides with the increase in the proportion of crustal-derived melts. The transcurrent tectonics seems to have played an essential role in the generation of mantle-derived magmas and may have facilitated their interaction with crustal melts which seem to be to a large extent the products of reworking of orthogneiss protoliths. (C) 2012 Elsevier B.V. All rights reserved.

G'day Gondwana - the final accretion of a supercontinent: U-Pb ages from the post-orogenic Sao Vicente Granite, northern Paraguay Belt, Brazil

The Paraguay Belt in central South America is part of a larger chain of orogenic belts, including the Araguaia Belt to the northeast and potentially the Pampean Belt to the south, which are believed to mark the suture zone of the Clymene Ocean - interpreted amongst the youngest of the Gondwana amalgamation orogens. The post-orogenic Sao Vicente Granite crops out in the northern Paraguay Belt and cuts the basal unit of the deformed and metamorphosed Cuiaba Group. The age of this granite therefore provides a long sort after minimum age for orogenesis within the belt. Dating crystallisation of this important intrusion is challenging due to the presence of considerable common-Pb. However, based on LA-ICPMS dating of more than 100 zircons from three separate samples we interpret a robust crystallisation age for the Sao Vicente batholith at 518 +/- 4 Ma. This age constrains the termination of deformation within the Paraguay Belt and the final accretion of the supercontinent Gondwana. (C) 2011 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.