Síntese e caracterização de materiais semicondutores nanoestruturados luminescentes à base de ZnS

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Biogenic calcium phosphate transformation in soils over millennial time scales

Changes in bioavailability of phosphorus (P) during pedogenesis and ecosystem development have been shown for geogenic calcium phosphate (Ca-P). However, very little is known about long-term changes of biogenic Ca-P in soil. Long-term transformation characteristics of biogenic Ca-P were examined using anthropogenic soils along a chronosequence from centennial to millennial time scales. Phosphorus fractionation of Anthrosols resulted in overall consistency with the Walker and Syers model of geogenic Ca-P transformation during pedogenesis. The biogenic Ca-P (e.g., animal and fish bones) disappeared to 3% of total P within the first ca. 2,000 years of soil development. This change concurred with increases in P adsorbed on metal-oxides surfaces, organic P, and occluded P at different pedogenic time. Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy revealed that the crystalline and therefore thermodynamically most stable biogenic Ca-P was transformed into more soluble forms of Ca-P over time. While crystalline hydroxyapatite (34% of total P) dominated Ca-P species after about 600-1,000 years, beta-tricalcium phosphate increased to 16% of total P after 900-1,100 years, after which both Ca-P species disappeared. Iron-associated P was observable concurrently with Ca-P disappearance. Soluble P and organic P determined by XANES maintained relatively constant (58-65%) across the time scale studied. Disappearance of crystalline biogenic Ca-P on a time scale of a few thousand years appears to be ten times faster than that of geogenic Ca-P.

Optimization of x-ray spectra in digital mammography through Monte Carlo simulations

In this work, a Monte Carlo code was used to investigate the performance of different x-ray spectra in digital mammography, through a figure of merit (FOM), defined as FOM = CNR2/(D) over bar (g), with CNR being the contrast-to-noise ratio in image and (D) over bar (g) being the average glandular dose. The FOM was studied for breasts with different thicknesses t (2 cm <= t <= 8 cm) and glandular contents (25%, 50% and 75% glandularity). The anode/filter combinations evaluated were those traditionally employed in mammography (Mo/Mo, Mo/Rh, Rh/Rh), and a W anode combined with Al or K-edge filters (Zr, Mo, Rh, Pd, Ag, Cd, Sn), for tube potentials between 22 and 34 kVp. Results show that the W anode combined with K-edge filters provides higher values of FOM for all breast thicknesses investigated. Nevertheless, the most suitable filter and tube potential depend on the breast thickness, and for t >= 6 cm, they also depend on breast glandularity. Particularly for thick and dense breasts, a W anode combined with K-edge filters can greatly improve the digital technique, with the values of FOM up to 200% greater than that obtained with the anode/filter combinations and tube potentials traditionally employed in mammography. For breasts with t < 4 cm, a general good performance was obtained with the W anode combined with 60 mu m of the Mo filter at 24-25 kVp, while 60 mu m of the Pd filter provided a general good performance at 24-26 kVp for t = 4 cm, and at 28-30 and 29-31 kVp for t = 6 and 8 cm, respectively.

Photoluminescence in silicon/silicon oxide films produced by the Pulsed Electron Beam Ablation technique

In this work we report studies of the photoluminescence emission in samples based on Si/SiOx films deposited by the Pulsed Electron Beam Ablation (PEBA) technique. The samples were prepared at room temperature using targets with different Si/SiO2 concentrations. The samples were characterized using X-ray Absorption Edge Spectroscopy (XANES) at the Si-K edge, Raman spectroscopy, Photoluminescence (PL) and X-ray Photoelectron Spectroscopy (XPS). The concentration of a-Si and nc-Si in the film was dependent on the silicon concentration in the target. It was also observed that the PL is strongly dependent on the structural amorphous/crystalline arrangement. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

Distribution of major elements in Atlantic surface sediments (36 degrees N-49 degrees S): Imprint of terrigenous input and continental weathering

Numerous studies use major element concentrations measured on continental margin sediments to reconstruct terrestrial climate variations. The choice and interpretation of climate proxies however differ from site to site. Here we map the concentrations of major elements (Ca, Fe, Al, Si, Ti, K) in Atlantic surface sediments (36 degrees N-49 degrees S) to assess the factors influencing the geochemistry of Atlantic hemipelagic sediments and the potential of elemental ratios to reconstruct different terrestrial climate regimes. High concentrations of terrigenous elements and low Ca concentrations along the African and South American margins reflect the dominance of terrigenous input in these regions. Single element concentrations and elemental ratios including Ca (e. g., Fe/Ca) are too sensitive to dilution effects (enhanced biological productivity, carbonate dissolution) to allow reliable reconstructions of terrestrial climate. Other elemental ratios reflect the composition of terrigenous material and mirror the climatic conditions within the continental catchment areas. The Atlantic distribution of Ti/Al supports its use as a proxy for eolian versus fluvial input in regions of dust deposition that are not affected by the input of mafic rock material. The spatial distributions of Al/Si and Fe/K reflect the relative input of intensively weathered material from humid regions versus slightly weathered particles from drier areas. High biogenic opal input however influences the Al/Si ratio. Fe/K is sensitive to the input of mafic material and the topography of Andean river drainage basins. Both ratios are suitable to reconstruct African and South American climatic zones characterized by different intensities of chemical weathering in well-understood environmental settings.

Novel SrTi1-xFexO3 nanocubes synthesized by microwave-assisted hydrothermal method

We report herein for the first time a facile synthesis method to obtain SrTi1-xFexO3 nanocubes by means by a microwave-assisted hydrothermal (MAH) method at 140 degrees C. The effect of iron addition on the structural and morphological properties of SrTiO3 was investigated. X-ray diffraction measurements show that all STFO samples present a cubic perovskite structure. X-ray absorption spectroscopy at Fe absorption K-edge measurements revealed that iron ions are in a mixed Fe2+/Fe3+ oxidation state and preferentially occupy the Ti4+-site. UV-visible spectra reveal a reduction in the optical gap (E-gap) of STFO samples as the amount of iron is increased. An analysis of the data obtained by field emission scanning electron microscopy points out that the nanoparticles present a cubic morphology independently of iron content. According to high-resolution transmission electron microscopy results, these nanocubes are formed by a self-assembly process of small primary nanocrystals.

EXAFS-Untersuchungen zur Rolle von Silicium bei der Sorption von umweltrelevanten Schwermetallen (Zn, As, Pb) in Speichermineralen (FeOOH,CSH)

Bei den Sorptions- und Desorptionsmechanismen an Mineraloberflächen ist oft nicht bekannt, durch welchen Mechanismus bestimmte Spurenelemente gebunden werden (Adsorption, Ionenaustausch, Ausfällung). Heterogene Reaktionen an der Fluid/Mineral-Grenzfläche sind im Allgemeinen sehr komplex. Ein Grund dafür ist, dass mehrere Mechanismen simultan ablaufen können. Da verschiedene Reaktionstypen räumlich getrennt ablaufen, d.h. im mikroskopischen Maßstab an unterschiedlichen Reaktionsplätzen, müssen die individuellen Reaktionsmechanismen auf atomarem Maßstab untersucht werden, um die Komplexität der Gesamtreaktion zu verstehen. Mit Hilfe der EXAFS Spektroskopie wurde die Bindungsform und -art der eingelagerten Zink- und Blei-Atome in die synthetische Calciumsilikathydratphase (CSH) und des adsorptiv gebundenen Arsens an der Oberfläche der natürlichen Eisenhydroxidphase bestimmt. Hierbei spielt Silizium eine relevante Rolle für die Immobilisierung von Schwermetallen. In beiden Fällen, in denen das Silizium einerseits als Adsorbat an der Oberfläche der Eisenhydroxidphase und andererseits in die Struktur der Mischphase gebunden vorliegt, trägt es wesentlich zur Form und Art der Bindung der Schwermetalle in die neugebildete Phase bei.

Ex situ X-­Ray absorption study of Li-­rich layered cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2

The Li-rich layered transition metal oxides (LLOs) Li2MnO3-LiMO2 (M=Mn, Co, Ni, etc.) have drawn considerable attention as cathode materials for rechargeable lithium batteries. They generate large reversible capacities but the fundamental reaction mechanism and structural perturbations during cycling remain controversial. In the present thesis, ex situ X-ray absorption spectroscopy (XAS) measurements were performed on Li[Li0.2Mn0.56Ni0.16Co0.08]O2 at different stage of charge during electrochemical oxidation/reduction. K-edge spectra of Co, Mn and Ni were recorded through a voltage range of 3.7-4.8V vs. Li/Li+, which consist of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Oxidation states during initial charge were discussed based on values from literature as well as XANES analysis. Information about bond distance, coordination number as well as corresponding Debye-Waller factor were extracted from Gnxas analysis of raw data in the EXAFS region. The possibility of oxygen participation in the initial charge was discussed. Co and Ni prove to take part in the oxidation/reduction process while Mn remain in the tetravalent state. The cathode material appears to retain good structural short-range order during charge-discharge. A resemblance of the pristine sample and sample 4 was discovered which was firstly reported for similar compounds.

Applicazioni dei fasci quasi-monocromatici in medicina

I raggi X, a partire dalla loro scoperta, avvenuta nel 1895 ad opera di Wilhelm Conrad Röntgen, si sono rivelati un potentissimo mezzo per lo studio della materia. In particolare in campo medico hanno permesso la nascita della diagnostica per immagini che, parallelamente allo sviluppo delle tecnologie, è diventata un mezzo imprescindibile per lo studio delle patologie. Negli ultimi decenni molti studi sono stati compiuti in particolare sui vantaggi dell’utilizzo nell’imaging di raggi X monocromatici in sostituzione dell’usuale radiazione policromatica. Con il seguente elaborato si ha l’intento di fornire un quadro generale sulla fisica dei raggi X, sulla loro interazione con la materia e sugli attuali metodi di produzione di fasci monocromatici e quasi-monocromatici, con particolare attenzione all'utilizzo su vasta scala. Sono state infine trattate le principali applicazioni della radiazione monocromatica e quasi-monocromatica nelle tecniche di imaging medico.

Dual-energy multidetector CT: how does it work, what can it tell us, and when can we use it in abdominopelvic imaging?

Dual-energy CT provides information about how substances behave at different energies, the ability to generate virtual unenhanced datasets, and improved detection of iodine-containing substances on low-energy images. Knowing how a substance behaves at two different energies can provide information about tissue composition beyond that obtainable with single-energy techniques. The term K edge refers to the spike in attenuation that occurs at energy levels just greater than that of the K-shell binding because of the increased photoelectric absorption at these energy levels. K-edge values vary for each element, and they increase as the atomic number increases. The energy dependence of the photoelectric effect and the variability of K edges form the basis of dual-energy techniques, which may be used to detect substances such as iodine, calcium, and uric acid crystals. The closer the energy level used in imaging is to the K edge of a substance such as iodine, the more the substance attenuates. In the abdomen and pelvis, dual-energy CT may be used in the liver to increase conspicuity of hypervascular lesions; in the kidneys, to distinguish hyperattenuating cysts from enhancing renal masses and to characterize renal stone composition; in the adrenal glands, to characterize adrenal nodules; and in the pancreas, to differentiate between normal and abnormal parenchyma.

Magnetic properties of ODP Site 175-1075

We present sediment magnetic and chemical analysis of cyclic ocean sediments of the upwelling region of the Lower Congo Basin (equatorial Atlantic). We investigated two >100-k.y. intervals from Ocean Drilling Program Site 1075 to analyze the hysteresis properties, sources of magnetic susceptibility, anhysteretic remanent magnetizations, thermomagnetic behavior, and element concentrations of Fe, Ca, Ti, Mn, and K using an X-ray fluorescence (XRF) core scanner. The upper interval was sampled between 14 and 32 meters composite depth (mcd; 0.09-0.21 Ma) and the lower between 141 and 163 mcd (1.31-1.54 Ma) at a resolution of 20 cm, which represents a temporal resolution of 2.0 and 1.3 k.y., respectively. XRF core-scanner data were acquired at 5-cm intervals. The measurements show that ferri(o)magnetic minerals have no significant influence on the cyclicity of the magnetic susceptibility, which is dominated by paramagnetic and diamagnetic minerals and reflects changes of sediment input from the Congo River. The Fe, Ti, K, and Mn concentrations covary with the magnetic susceptibility where high concentrations of these elements correlate with intervals of high susceptibility and low concentrations with intervals of low susceptibility. The Ca counts correlate well with the calcium carbonate concentration but do not show the same cyclicity as the other elements or the susceptibility. With the exception of the Ca concentration, which is significantly higher in the upper interval, and the magnetic grain size, which indicates that less fine grained magnetite is present in the lower interval, no significant differences in the properties of the upper and the lower intervals were detected.

Mineralogy micromorphology, and geochemistry at DSDP Site 89-585

At Site 585 of Deep Sea Drilling Project Leg 89 more than 500 m of volcaniclastic to argillaceous middle-Late Cretaceous sediments were recovered. Analyses by X-ray diffraction (bulk sediment and clay fraction), transmission electron microscopy, molecular and atomic absorption, and electron microprobe were done on Site 585 samples. We identify four successive stages and interpret them as the expression of environments evolving under successive influences: Stage 1, late Aptian to early Albian - subaerial and proximal volcanism, chiefly expressed by the presence of augite, analcite, olivine, celadonite, small and well-shaped transparent trioctahedral saponite, Al hydroxides, Na, Fe, Mg, and various trace elements (Mn, Ni, Cr, Co, Pb, V, Zn, Ti). Stage 2, early to middle Albian - submarine and less proximal volcanic influence, characterized by dioctahedral and hairy Mg-beidellites, a paucity of analcite and pyroxenes, the presence of Mg and K, and local alteration of Mg-smectites to Mg-chlorites. Stage 3, middle Albian to middle Campanian - early marine diagenesis, marked by the development of recrystallization from fleecy smectites to lathed ones (all of alkaline Si-rich Fe-beidellite types), by the development of opal CT and clinoptilolite, and by proximal to distal volcanic influences (Na parallel to Ti, K). Local events consist of the supply of reworked palygorskite during the Albian-Cenomanian, and the recurrence of proximal volcanic activity during the early Campanian. Stage 4, late Campanian to Maestrichtian - development of terrigenous supply resulting from the submersion of topographic barriers; this terrigenous supply is associated with minor diagenetic effects and is marked by a clay diversification (beidellite, illite, kaolinite, palygorskite), the rareness of clay recrystallizations, and the disappearance of volcanic markers.

Controls of sediment dynamics on the Galician slope reconstructed from three sediment cores (GeoB11035-1, GeoB130206-1, GeoB13071-1)

Controls of sediment dynamics at the Galician continental slope (NW Iberia) during the past 30 ka were reconstructed from three new gravity cores (GeoB11035-1, 130206-1, 13071-1) based on sedimentological (e.g. sortable silt, IRD), micropalaeontological (e.g. coccoliths), geochemical (AMS 14C, XRF) and geophysical (e.g. magnetic susceptibility) diagnostics. The data are consistent with existing regional knowledge that, during marine isotope stages 3-1, variations in detrital input, marine productivity and sea level were the essential drivers of sediment availability on the slope, whereas deep-water current velocities controlled sediment deposition: (1) the period prior to 30 cal ka BP is characterized by minor but systematic variations in various proxies which can be associated with D-O cycles; (2) between 30 and 18 cal ka BP, high detrital input and steady slope-parallel currents led to constant sedimentation; (3) from the LGM until 10 cal ka BP, the shelf-transgressive sea-level rise increased the detrital particle flux; sedimentation was influenced by significantly enhanced deep-water circulation during the Bølling/Allerød, and subsequent slowing during the Younger Dryas; (4) an abrupt and lasting change to hemipelagic sedimentation at ca. 10 cal ka BP was probably due to Holocene warming and decelerated transgression; (5) after 5 cal ka BP, additional input of detrital material to the slope is plausibly linked to the evolution of fine-grained depocentres on the Galician shelf, this being the first report of this close shelf-slope sedimentary linkage off NW Iberia. Furthermore, there is novel evidence of the nowadays strong outer shelf Iberian Poleward Current becoming established at about 15.5 cal ka BP. The data also demonstrate that small-scale morphologic features and local pathways of sediment export from the neighbouring shelf play an important role for sediment distribution on the NW Iberian slope, including a hitherto unknown sediment conduit off the Ría de Arousa. By implication, the impact of local morphology on along- and down-slope sediment dynamics is more complex than commonly considered, and deserves future attention.

(Table 1) Basalt geochemsitry at DSDP Hole 72-516F

Basalts from Hole 516F, DSDP Leg 72 on the Rio Grande Rise are tholeiitic in character but differ from normal mid-ocean ridge basalts in the South Atlantic in higher concentrations of incompatible elements such as Ti, K, V, Sr, Ba, Zr, Nb, and light rare-earth elements and in lower concentrations of Mg, Cr, and Ni. They contrast with previously reported basalts from the Rio Grande Rise, which were highly alkalic in character. The Rio Grande Rise basalts from Hole 516F (age 84.5 Ma) are generally similar to basalts from the eastern end of the Walvis Ridge (80-100 Ma). It is suggested that they either originated, like the Walvis Ridge, from a mantle hot spot that is different from the present-day hot spot (Tristan da Cunha) and that has changed composition with time, or from a spreading center that was shallow and chemically influenced by the adjacent hot spot, similar to the present-day Mid-Atlantic Ridge near the Azores and Tristan da Cunha.

Climatic records of the late Holocene from sediment core GeoB9504-3 off Senegal

High-resolution climatic records of the late Holocene along the north-west African continental margin are scarce. Here we combine sediment grain size, elemental distribution and mineral assemblage data to trace dust and riverine sources at a shallow-marine sediment depocentre in the vicinity of the Senegal River mouth. The aim is to understand how these terrigenous components reflect climate variability during the late Holocene. Major element contents were measured and mineral identification was performed on three sub-fractions of our sediment core: (i) fluvial material <2 µm, (ii) aeolian material of 18-63 µm and (iii) a sub-fraction of dual-origin material of 2-18 µm. Results show that more than 80% of the total Al and Fe terrigenous bulk content is present in the fluviogenic fraction. In contrast, Ti, K and Si cannot be considered as proxies for one specific source off Senegal. The Al/Ca ratio, recording the continental river runoff, reveals two dry periods from 3010 to 2750 cal a BP and from 1900 to 1000 cal a BP, and two main humid periods from 2750 to 1900 cal a BP and from 1000 to 700 cal a BP. The match between (i) intervals of low river runoff inferred by low Al/Ca values, (ii) reduced river discharge inferred by integrated palynological data from offshore Senegal and (iii) periods of enhanced dune reactivation in Mali confirms this interpretation.