Showing papers by "National Nuclear Energy Commission published in 2017"

Type I and Type II Photosensitized Oxidation Reactions: Guidelines and Mechanistic Pathways

Abstract: Here, 10 guidelines are presented for a standardized definition of type I and type II photosensitized oxidation reactions. Because of varied notions of reactions mediated by photosensitizers, a checklist of recommendations is provided for their definitions. Type I and type II photoreactions are oxygen-dependent and involve unstable species such as the initial formation of radical cation or neutral radicals from the substrates and/or singlet oxygen (1 O21 ∆g ) by energy transfer to molecular oxygen. In addition, superoxide anion radical (O2·-) can be generated by a charge-transfer reaction involving O2 or more likely indirectly as the result of O2 -mediated oxidation of the radical anion of type I photosensitizers. In subsequent reactions, O2·- may add and/or reduce a few highly oxidizing radicals that arise from the deprotonation of the radical cations of key biological targets. O2·- can also undergo dismutation into H2 O2 , the precursor of the highly reactive hydroxyl radical (·OH) that may induce delayed oxidation reactions in cells. In the second part, several examples of type I and type II photosensitized oxidation reactions are provided to illustrate the complexity and the diversity of the degradation pathways of mostly relevant biomolecules upon one-electron oxidation and singlet oxygen reactions.

Large emissions from floodplain trees close the Amazon methane budget

Abstract: Wetlands are the largest global source of atmospheric methane (CH4), a potent greenhouse gas. However, methane emission inventories from the Amazon floodplain, the largest natural geographic source of CH4 in the tropics, consistently underestimate the atmospheric burden of CH4 determined via remote sensing and inversion modelling, pointing to a major gap in our understanding of the contribution of these ecosystems to CH4 emissions. Here we report CH4 fluxes from the stems of 2,357 individual Amazonian floodplain trees from 13 locations across the central Amazon basin. We find that escape of soil gas through wetland trees is the dominant source of regional CH4 emissions. Methane fluxes from Amazon tree stems were up to 200 times larger than emissions reported for temperate wet forests and tropical peat swamp forests, representing the largest non-ebullitive wetland fluxes observed. Emissions from trees had an average stable carbon isotope value (δ13C) of -66.2 ± 6.4 per mil, consistent with a soil biogenic origin. We estimate that floodplain trees emit 15.1 ± 1.8 to 21.2 ± 2.5 teragrams of CH4 a year, in addition to the 20.5 ± 5.3 teragrams a year emitted regionally from other sources. Furthermore, we provide a 'top-down' regional estimate of CH4 emissions of 42.7 ± 5.6 teragrams of CH4 a year for the Amazon basin, based on regular vertical lower-troposphere CH4 profiles covering the period 2010-2013. We find close agreement between our 'top-down' and combined 'bottom-up' estimates, indicating that large CH4 emissions from trees adapted to permanent or seasonal inundation can account for the emission source that is required to close the Amazon CH4 budget. Our findings demonstrate the importance of tree stem surfaces in mediating approximately half of all wetland CH4 emissions in the Amazon floodplain, a region that represents up to one-third of the global wetland CH4 source when trees are combined with other emission sources.

Effect of the type of ceria dopant on the performance of Ni/CeO2 SOFC anode for ethanol internal reforming

Abstract: This work studied the effect of the type of ceria dopant on the performance of Ni/CeO2 SOFC anode for ethanol conversion reaction. Ni-based catalysts supported on CeO2 doped with different cations (Gd, Y, Pr, Zr, Nb) were prepared by the hydrothermal method. The addition of dopant to ceria led to the formation of the solid solutions during calcination for all samples, except for CeNb sample due to the low solubility limit. In spite of the high oxygen mobility of ceria-based supports, all catalysts deactivated for ethanol decomposition reaction at 1123 K due to carbon deposition. The large Ni0 and CeO2 crystallites formed during calcination at high temperature reduced the effectiveness of the mechanism of carbon removal because of the low metal-support interfacial area. The lowest formation of carbon on Ni/CeNb catalyst was attributed to the presence of NiNb2O6 phase. The reduction of this phase leads to the formation of Ni particles covered by NbOx species, which inhibits carbon formation.

Distribution of growth hormone-responsive cells in the mouse brain

Abstract: Growth hormone (GH) exerts important biological effects primarily related to growth and metabolism. However, the role of GH signaling in the brain is still elusive. To better understand GH functions in the brain, we mapped the distribution of GH-responsive cells and identified the receptors involved in GH central effects. For this purpose, mice received an acute intraperitoneal challenge with specific ligands of the GH receptor (mouse GH), prolactin receptor (prolactin) or both receptors (human GH), and their brains were subsequently processed immunohistochemically to detect the phosphorylated form of STAT5 (pSTAT5). GH induced pSTAT5 immunoreactivity in neurons, but not in astroglial cells of numerous brain regions, including the cerebral cortex, nucleus accumbens, hippocampus, septum and amygdala. The most prominent populations of GH-responsive neurons were located in hypothalamic areas, including several preoptic divisions, and the supraoptic, paraventricular, suprachiasmatic, periventricular, arcuate, ventromedial, dorsomedial, tuberal, posterior and ventral premammillary nuclei. Interestingly, many brainstem structures also exhibited GH-responsive cells. Experiments combining immunohistochemistry for pSTAT5 and in situ hybridization for GH and prolactin receptors revealed that human GH induced pSTAT5 in most, but not all, brain regions through both prolactin and GH receptors. Additionally, males and females exhibited a similar number of GH-responsive cells in forebrain structures known to be sexually dimorphic. In summary, we found GH-responsive cells primarily distributed in brain regions implicated in neurovegetative, emotional/motivational and cognitive functions. Our findings deepen the understanding of GH signaling in the brain and suggest that central GH signaling is likely more ample and complex than formerly recognized.

Synthesis of Pt+SnO2/C electrocatalysts containing Pt nanoparticles with preferential (100) orientation for direct ethanol fuel cell

Abstract: The synthesis of Pt + SnO2/C electrocatalyst containing cubic Pt nanoparticles with preferential (100) orientation was performed by an alcohol-reduction process using KBr as a shape directing agent. The order of addition of the Pt and Sn precursors and KBr was crucial to obtain cubic Pt particles and a SnO2 phase with small particle sizes highly dispersed on the carbon support. Electrochemical and DEFC experiments showed that Pt + SnO2/C electrocatalyst containing Pt nanoparticles with preferential (100) orientation provided superior activity for EOR, power densities and CO2 selectivity compared to Pt + SnO2/C electrocatalyst containing Pt polycrystalline.

Mangiferin functionalized radioactive gold nanoparticles (MGF-198AuNPs) in prostate tumor therapy: green nanotechnology for production, in vivo tumor retention and evaluation of therapeutic efficacy.

Abstract: We report here an innovative feature of green nanotechnology-focused work showing that mangiferin—a glucose functionalized xanthonoid, found in abundance in mango peels—serves dual roles of chemical reduction and in situ encapsulation, to produce gold nanoparticles with optimum in vivo stability and tumor specific characteristics. The interaction of mangiferin with a Au-198 gold precursor affords MGF-198AuNPs as the beta emissions of Au-198 provide unique advantages for tumor therapy while gamma rays are used for the quantitative estimation of gold within the tumors and various organs. The laminin receptor specificity of mangiferin affords specific accumulation of therapeutic payloads of this new therapeutic agent within prostate tumors (PC-3) of human prostate tumor origin induced in mice which overexpress this receptor subtype. Detailed in vivo therapeutic efficacy studies, through the intratumoral delivery of MGF-198AuNPs, show the retention of over 80% of the injected dose (ID) in prostate tumors up to 24 h. By three weeks post treatment, tumor volumes of the treated group of animals showed an over 5 fold reduction as compared to the control saline group. New opportunities for green nanotechnology and a new paradigm of using mangiferin as a tumor targeting agent in oncology for the application of MGF-198AuNPs in the treatment of cancer are discussed.

Production of Biochar, Bio-Oil and Synthesis Gas from Cashew Nut Shell by Slow Pyrolysis

Abstract: Cashew nut shell waste from northeast region of Brazil was characterized and slow pyrolyzed in a simple batch type reactor heated externally by liquefied petroleum gas as fuel. The experiments were performed using nitrogen or air as carrier gases. The properties of biochar, bio-oil and gases products were investigated and potential applications were proposed. Cashew nut shell showed a high heating value of 20.7 MJ kg−1 that is among the highest found for different types of biomass. Pyrolysis under nitrogen flow showed a yield of solid, liquid and gas products of about 30, 40 and 30 wt%, respectively. Under air flow an increase of gas phase (46 wt%) was observed with a decrease in the production of biochar and, mainly bio-oil. The biochars have high contents of carbon (70–75 wt%) and high heating values in the range of 25–28 MJ kg−1 presenting suitable properties for use as energy source. Biochars also contain significant quantities of K and minor amounts of Mg, Ca, Cu, Zn and Fe showing potential as fertilizer. The bio-oils showed high heating values of about 32 MJ kg−1 and are not suitable for use in pure form, but can be used in mixtures with Diesel (42.5 MJ kg−1). The gas phase revealed the predominance of CO2 and CO at temperatures lower than 400 °C and, above this temperature, there was a preferential formation of H2 resulting in synthesis gas with different compositions that could be burned to supply heat for the pyrolysis process and/or to produce organic chemicals.

A global synthesis inversion analysis of recent variability in CO 2 fluxes using GOSAT and in situ observations

Abstract: . The precise contribution of the two major sinks for anthropogenic CO2 emissions, terrestrial vegetation and the ocean, and their location and year-to-year variability are not well understood. Top-down estimates of the spatiotemporal variations in emissions and uptake of CO2 are expected to benefit from the increasing measurement density brought by recent in situ and remote CO2 observations. We uniquely apply a batch Bayesian synthesis inversion at relatively high resolution to in situ surface observations and bias-corrected GOSAT satellite column CO2 retrievals to deduce the global distributions of natural CO2 fluxes during 2009–2010. The GOSAT inversion is generally better constrained than the in situ inversion, with smaller posterior regional flux uncertainties and correlations, because of greater spatial coverage, except over North America and northern and southern high-latitude oceans. Complementarity of the in situ and GOSAT data enhances uncertainty reductions in a joint inversion; however, remaining coverage gaps, including those associated with spatial and temporal sampling biases in the passive satellite measurements, still limit the ability to accurately resolve fluxes down to the sub-continental or sub-ocean basin scale. The GOSAT inversion produces a shift in the global CO2 sink from the tropics to the north and south relative to the prior, and an increased source in the tropics of ∼ 2 Pg C yr −1 relative to the in situ inversion, similar to what is seen in studies using other inversion approaches. This result may be driven by sampling and residual retrieval biases in the GOSAT data, as suggested by significant discrepancies between posterior CO2 distributions and surface in situ and HIPPO mission aircraft data. While the shift in the global sink appears to be a robust feature of the inversions, the partitioning of the sink between land and ocean in the inversions using either in situ or GOSAT data is found to be sensitive to prior uncertainties because of negative correlations in the flux errors. The GOSAT inversion indicates significantly less CO2 uptake in the summer of 2010 than in 2009 across northern regions, consistent with the impact of observed severe heat waves and drought. However, observations from an in situ network in Siberia imply that the GOSAT inversion exaggerates the 2010–2009 difference in uptake in that region, while the prior CASA-GFED model of net ecosystem production and fire emissions reasonably estimates that quantity. The prior, in situ posterior, and GOSAT posterior all indicate greater uptake over North America in spring to early summer of 2010 than in 2009, consistent with wetter conditions. The GOSAT inversion does not show the expected impact on fluxes of a 2010 drought in the Amazon; evaluation of posterior mole fractions against local aircraft profiles suggests that time-varying GOSAT coverage can bias the estimation of interannual flux variability in this region.

Random Lasing at Localization Transition in a Colloidal Suspension (TiO2@Silica)

Abstract: Anderson localization of light and random lasing in this critical regime is an open research frontier, which besides being a basic research topic could also lead to important applications This article investigates the random laser action at the localization transition in a strongly disordered scattering medium composed of a colloidal suspension of core–shell nanoparticles (TiO2@Silica) in ethanol solution of Rhodamine 6G The classical superfluorescence band of the random laser was measured separately by collecting the emission at the back of the samples, showing a linear dependence with pumping fluence without gain depletion However, frontal collection showed saturation of the absorption and emission Narrow peaks of approximately equal intensity are observed on top of the classical superfluorescence band, indicating suppression of the interaction between the peaks modes The linewidth of these peaks is lower than that of the passive modes of the scattering medium A method called fraction of absorbed

Modeling the radiative effects of biomass burning aerosols on carbon fluxes in the Amazon region

Abstract: . Every year, a dense smoke haze covers a large portion of South America originating from fires in the Amazon Basin and central parts of Brazil during the dry biomass burning season between August and October. Over a large portion of South America, the average aerosol optical depth at 550 nm exceeds 1.0 during the fire season, while the background value during the rainy season is below 0.2. Biomass burning aerosol particles increase scattering and absorption of the incident solar radiation. The regional-scale aerosol layer reduces the amount of solar energy reaching the surface, cools the near-surface air, and increases the diffuse radiation fraction over a large disturbed area of the Amazon rainforest. These factors affect the energy and CO2 fluxes at the surface. In this work, we applied a fully integrated atmospheric model to assess the impact of biomass burning aerosols in CO2 fluxes in the Amazon region during 2010. We address the effects of the attenuation of global solar radiation and the enhancement of the diffuse solar radiation flux inside the vegetation canopy. Our results indicate that biomass burning aerosols led to increases of about 27 % in the gross primary productivity of Amazonia and 10 % in plant respiration as well as a decline in soil respiration of 3 %. Consequently, in our model Amazonia became a net carbon sink; net ecosystem exchange during September 2010 dropped from +101 to −104 TgC when the aerosol effects are considered, mainly due to the aerosol diffuse radiation effect. For the forest biome, our results point to a dominance of the diffuse radiation effect on CO2 fluxes, reaching a balance of 50–50 % between the diffuse and direct aerosol effects for high aerosol loads. For C3 grasses and savanna (cerrado), as expected, the contribution of the diffuse radiation effect is much lower, tending to zero with the increase in aerosol load. Taking all biomes together, our model shows the Amazon during the dry season, in the presence of high biomass burning aerosol loads, changing from being a source to being a sink of CO2 to the atmosphere.

Mapping soil radioactivity in the Fernando de Noronha archipelago, Brazil

Abstract: A radioactivity survey was conducted on some of the most alkaline volcanic islands in the world. Seventy soil samples were analysed using gamma spectrometry. 226Ra, 232Th, 40K and 137Cs (Bq kg−1) activity concentration varied from 4.6 to 550, 10 to 298, 13 to 1280 and <0.3 to 2.0, respectively. Although the concentration ranges for 232Th (228Ra) and 226Ra exceeded the worldwide range, 40K levels remained low. The lowest values of natural radionuclides were observed over the Quixaba Formation, and the highest values were observed over the Remedios Formation. The median effective dose from external radiation exposure was 0.45 mSv a−1.

The relationship between aerosol particles chemical composition and optical properties to identify the biomass burning contribution to fine particles concentration: a case study for São Paulo city, Brazil

Abstract: The air quality in the Metropolitan Area of Sao Paulo (MASP) is primarily determined by the local pollution source contribution, mainly the vehicular fleet, but there is a concern about the role of remote sources to the fine mode particles (PM2.5) concentration and composition. One of the most important remote sources of atmospheric aerosol is the biomass burning emissions from Sao Paulo state’s inland and from the central and north portions of Brazil. This study presents a synergy of different measurements of atmospheric aerosol chemistry and optical properties in the MASP in order to show how they can be used as a tool to identify particles from local and remote sources. For the clear identification of the local and remote source contribution, aerosol properties measurements at surface level were combined with vertical profiles information. Over 15 days in the austral winter of 2012, particulate matter (PM) was collected using a cascade impactor and a Partisol sampler in Sao Paulo City. Mass concentrations were determined by gravimetry, black carbon concentrations by reflectance, and trace element concentrations by X-ray fluorescence. Aerosol optical properties were studied using a multifilter rotating shadowband radiometer (MFRSR), a Lidar system and satellite data. Optical properties, concentrations, size distributions, and elemental composition of atmospheric particles were strongly related and varied according to meteorological conditions. During the sampling period, PM mean mass concentrations were 17.4 ± 10.1 and 15.3 ± 6.9 μg/m3 for the fine and coarse fractions, respectively. The mean aerosol optical depths at 415 nm and Angstrom exponent (AE) over the whole period were 0.29 ± 0.14 and 1.35 ± 0.11, respectively. Lidar ratios reached values of 75 sr. The analyses of the impacts of an event of biomass burning smoke transport to the Sao Paulo city revealed significant changing on local aerosol concentrations and optical parameters. The identification of the source contributions, local and remote, to the fine particles in MASP can be more precisely achieved when particle size composition and distribution, vertical profile of aerosols, and air mass trajectories are analyzed in combination.

Progression of erosive lesions after Nd:YAG laser and fluoride using optical coherence tomography.

Abstract: This study aimed to use optical coherence tomography (OCT) to assess the progression of erosive lesions after irradiation with Nd:YAG laser and application of topical fluoride. One-hundred and twenty dentin samples (4 × 4 × 2 mm) obtained from bovine incisors were used. Samples were protected with acid-resistant nail varnish, with exception of a central circular area 2 mm in diameter. All samples were submitted to erosive cycles with citric acid solution 0.05 M (citric acid monohydrate—C6H8O7·H2O); M = 210.14 g/mol) pH 2.3, at room temperature, for 20 min, 2×/day, throughout 20 days. After 10 days of acid challenges, lesions became visible, and each group received a different treatment (n = 15): control (without treatment), topical application of sodium fluoride 2 % for 4 min; Nd:YAG laser with different irradiation parameters (1, 0.7, and 0.5 W); and the association of fluoride with the laser parameters. OCT readouts were performed on day 01 (before the first acid challenge—OCT1), on day 05 (OCT2), day 10 (OCT3—after treatment), day 15 (OCT4), day 17 (OCT5), and day 20 (OCT6). The OCT images generated made it possible to measure the amount of tooth tissue loss over the 20 days of erosive cycle, before and after treatments, and to monitor early dentin demineralization progression. After statistical analysis, the fluoride group was observed to be the one that showed smaller loss of tissue over time. The OCT technique is promising for diagnosing and monitoring erosive lesion damage; however, further in vitro and in vivo research is needed to improve its use.

A Brazilian coal fly ash as a potential source of rare earth elements

Abstract: Rare earth elements (REEs) have several applications and their market demands have increased. Recently, coal fly ash (CFA) has been considered as a source of these elements. The purpose of this study was to evaluate the REEs content in a CFA from a Brazilian coal power plant by instrumental neutron analysis, to classify it according to commercial purposes and to assess the weathering impact in the REEs content, since it is held in fields nearby the power plant. The results pointed no significant REEs leachability and indicated this CFA as a promising REEs source.