Accumulation of six metals in the mangrove crab Ucides cordatus (Crustacea: Ucididae) and its food source, the red mangrove Rhizophora mangle (Angiosperma: Rhizophoraceae)

The crab Ucides cordatus and the red mangrove Rhizophora mangle are endemic mangrove species and potential bio-accumulators of metals. This study quantified the accumulation of six metals (Cd, Cr, Cu, Hg, Mn and Pb) in different organs (claw muscle, hepatopancreas and gills) of U. cordatus, as well as in different maturation stages of the leaves (buds, green mature, and pre-abscission senescent) of R. mangle. Samples were collected from mangrove areas in Cubatao, state of São Paulo, a heavily polluted region in Brazil. Data for metal contents in leaves were evaluated by one-way ANOVA; while for crabs a factorial ANOVA was used to investigate the effect of different tissues, animal size and the interactions between them. Means were compared by Tukey test at five percent, and the association between the metal concentrations in each crab organ, depending on the size, was evaluated by Pearson's linear correlation coefficient (r). Concentrations of Pb and Hg were undetectable for the different leaf stages and crab tissues, while Cd concentrations were undetectable in the leaf stages. In general, the highest accumulation of metals in R. mangle leaves occurred in pre-abscission senescent and green mature leaves, except for Cu, which was found in the highest concentrations in buds and green mature leaves. For the crab, Cd, Cu, Cr and Mn were present in concentrations above the detection limit, with the highest accumulation in the hepatopancreas, followed by the gills. Cu was accumulated mostly in the gills. Patterns of bioaccumulation between the crab and the mangrove tree differed for each metal, probably due to the specific requirements of each organism for essential metals. However, there was a close and direct relationship between metal accumulation in the mangrove trees and in the crabs feeding on them. Tissues of R. mangle leaves and U. cordatus proved effective for monitoring metals, acting as important bioindicators of mangrove areas contaminated by various metals. (C) 2012 Elsevier B.V. All rights reserved.

Avaliação da correlação entre os parâmetros, carbono orgânico total e elementos tóxicos, em solo de um posto de serviço e revenda de combustíveis

Today a major responsibility for the contamination of soil and groundwater and surface water are establishments known as gas stations of fuel which has attracted increasing attention from both the general population as the state agencies of environmental control due to leaks in storage tanks and mainly to disruption of pipe corrosion of tanks and pumping. Other services, like oil changes and car wash are also causes for concern in this type of establishment. These leaks can cause or waste produced, and the contamination of aquifers, serious health problems and public safety, since most of these stations located in urban areas. Based on this, the work was to evaluate soil contamination of a particular service station and fuel sales in the city of Natal, through the quantification of heavy metals like Cd, Cu, Cr, Ni, Pb, Zn of total organic carbon (TOC) and organic matter using different techniques such as optical emission spectrometry with inductively coupled plasma source (ICP OES), Total Organic Carbon analyzer and gravimetric analysis respectively. And also to characterize the soil through particle size analysis. Samples were taken in 21 georeferenced points and collected in the same period. The soils sampled in sampling stations P3, P5, P6, P10, P11, P12, P13, P14, P15, P17, P18 and P20 showed the smallest size fractions ranging from fine sand to medium sand. The other study sites ranged from fine sand to medium sand, except the point P8 showed that only the type size medium sand and P19, indicating a particle size of the coarse type. The small correlation of organic matter with the elements studied in this work suggests that these are not of anthropogenic origin but geochemical support

Détermination de la spéciation du samarium dans l'environnement

Les éléments de terres rares (REEs) sont de plus en plus utilisés dans une multitude d’applications, notamment la fabrication d’aimants, de batteries rechargeables et les écrans de téléviseurs. Ils sont pour la plupart des métaux trivalents peu solubles dans les eaux naturelles. Comme pour les métaux divalents, le risque écologique des REEs est très probablement étroitement lié à leurs spéciations chimiques. Cependant, le comportement du samarium (Sm) dans les matrices environnementales est très peu connu et il n'existe actuellement aucune technique pour évaluer sa spéciation chimique. Dans cette optique, la technique d'échange d'ions (IET) sur la résine Dowex a été optimisée pour mesurer le samarium libre en solution. Les temps d'équilibre ont d'abord été déterminés pour des solutions tamponnées de samarium (Sm 6,7x10-8 M ; MES 1,0 mM M ; pH 6,0) en présence du nitrate de sodium (de 0,01M à 0,5 M). Pour ces diverses forces ioniques, l’équilibre thermodynamique n’est atteint que pour NaNO3 0,5M. Un autre mode d’utilisation de la résine (mode dynamique) a donc été développé pour tenir compte des conditions environnementales et évaluer efficacement le samarium libre. Les impacts des ligands organiques tels le NTA, l’EDTA, le citrate, l’acide malique et l’acide fulvique Suwannee River Standard I (SRFA) ont été étudiés par l’IET en mode dynamique. Une grande corrélation a été trouvée plus entre les taux d’accumulation de samarium sur la résine d’échange pour différents rapports NTA : Sm, EDTA : Sm, SRFA : Sm et le samarium libre. Par contre, aucune corrélation significative n’a été observée pour les ligands citrate et acide malique compte tenu des complexes qu’ils forment avec le samarium et qui s’adsorbent aussi sur la résine Dowex. Les concentrations Sm3+ mesurées par la technique IET ont été fortement corrélées avec celles prédites par le modèle WHAM 7.0 en utilisant la constante de stabilité obtenue par titration de SRFA par extinction de la fluorescence. Par ailleurs, la formation de colloïdes de samarium en fonction du pH influe grandement sur la détermination du samarium libre et doit être prise en compte dans la spéciation du samarium. L'IET assisté par des techniques auxiliaires comme le dosage par extinction de la fluorescence et le SP-ICPMS pourrait être une technique utile pour évaluer les concentrations de Sm biodisponible dans les eaux naturelles.

Détermination de la spéciation du samarium dans l'environnement

Les éléments de terres rares (REEs) sont de plus en plus utilisés dans une multitude d’applications, notamment la fabrication d’aimants, de batteries rechargeables et les écrans de téléviseurs. Ils sont pour la plupart des métaux trivalents peu solubles dans les eaux naturelles. Comme pour les métaux divalents, le risque écologique des REEs est très probablement étroitement lié à leurs spéciations chimiques. Cependant, le comportement du samarium (Sm) dans les matrices environnementales est très peu connu et il n'existe actuellement aucune technique pour évaluer sa spéciation chimique. Dans cette optique, la technique d'échange d'ions (IET) sur la résine Dowex a été optimisée pour mesurer le samarium libre en solution. Les temps d'équilibre ont d'abord été déterminés pour des solutions tamponnées de samarium (Sm 6,7x10-8 M ; MES 1,0 mM M ; pH 6,0) en présence du nitrate de sodium (de 0,01M à 0,5 M). Pour ces diverses forces ioniques, l’équilibre thermodynamique n’est atteint que pour NaNO3 0,5M. Un autre mode d’utilisation de la résine (mode dynamique) a donc été développé pour tenir compte des conditions environnementales et évaluer efficacement le samarium libre. Les impacts des ligands organiques tels le NTA, l’EDTA, le citrate, l’acide malique et l’acide fulvique Suwannee River Standard I (SRFA) ont été étudiés par l’IET en mode dynamique. Une grande corrélation a été trouvée plus entre les taux d’accumulation de samarium sur la résine d’échange pour différents rapports NTA : Sm, EDTA : Sm, SRFA : Sm et le samarium libre. Par contre, aucune corrélation significative n’a été observée pour les ligands citrate et acide malique compte tenu des complexes qu’ils forment avec le samarium et qui s’adsorbent aussi sur la résine Dowex. Les concentrations Sm3+ mesurées par la technique IET ont été fortement corrélées avec celles prédites par le modèle WHAM 7.0 en utilisant la constante de stabilité obtenue par titration de SRFA par extinction de la fluorescence. Par ailleurs, la formation de colloïdes de samarium en fonction du pH influe grandement sur la détermination du samarium libre et doit être prise en compte dans la spéciation du samarium. L'IET assisté par des techniques auxiliaires comme le dosage par extinction de la fluorescence et le SP-ICPMS pourrait être une technique utile pour évaluer les concentrations de Sm biodisponible dans les eaux naturelles.

Quasicrystals and their crystalline homologues in the Al-Mn-Cu ternary alloys

Electron diffraction and high-resolution electron microscopy have been employed to differentiate among icosahedral, decagonal and crystalline particles that occur in as-cast and rapidly solidified Al-Mn-Cu alloys. The resemblance between decagonal quasicrystals and crystals in their electron diffraction patterns is striking. The crystalline structure is based on the orthorhombic 'Al3Mn' structure, but also a new monoclinic phase called 'X' has been discovered and described here. The present observations are also closely related to the orthorhombic structures in Al60Mn11Ni4. The occurrence of fine-scale twinning and fragmentation into domains explains the complex diffraction effects.

Effect of Nb Content on the Microstructure and Mechanical Properties of Zr-Cu-Ni-Al-Nb Glass Forming Alloys

(Zr65Al10Ni10Cu15)(100-x) Nb-x glass forming alloys with Nb contents ranging from 0 to 15 at.% were prepared by water-cooled copper mould cast. The alloys with different Nb contents exhibited different microstructures and mechanical properties. Unlike the monolithic Zr65Al10Ni10Cu15 bulk metallic glass, only a few primary bee beta-Ti phase dendrites were found to distribute in the glassy matrix of the alloys with x = 5. For alloys with x = 10, more beta-phase dendrites forms, together with quasicrystalline particles densely distributed in the matrix of the alloys. For alloys with x = 15, the microstructure of the alloy is dominated by a high density of fully developed P-phase dendrites and the volume fraction of quasicrystalline particles significantly decreases. Room temperature compression tests showed that the alloys with x = 5 failed at 1793 MPa and exhibited an obvious plastic strain of 3.05%, while the other samples all failed in a brittle manner. The ultimate fracture strengths are 1793, 1975 and 1572 MPa for the alloys with x = 0, 10 and 15 at.% Nb, respectively.

Simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by GFAAS

A method has been developed for the simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by graphite furnace atomic absorption spectrometry (GFAAS) using a transversely heated graphite atomizer (THGA) with longitudinal Zeeman-effect background correction. The thermal behavior of analytes during the pyrolysis and atomization stages using the mixture Pd(NO3)(2) + Mg(NO3)(2) as the chemical modifier was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3, and diluted ethanol (1 + 1, v/v) containing different nitric acid concentrations. With 5 rhog Pd + 3 mug Mg as the modifiers, pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1200 C and 2200degreesC respectively. For 20 muL of diluted sample (10 muL ethanol + 10 muL of 0.28 mol L-1 HNO3) dispensed into the graphite tube, analytical curves in the 2.0 - 50 mug L-1 Al, As, Cu, Fe, Mn, Ni ranges were established. The calculated characteristic masses were - 37 pg Al, 73 pg As, 31 pg Cu, 16 pg Fe, 9 pg Mn, and 44 pg Ni, and the lifetime of the tube was around 2 50 firings. The limits of detection (LOD) based on integrated absorbance were 1.2 mug L-1 Al, 2.5 mug L-1 As. 0.22 mug L-1 Cu, 1.6 L-1 Fe 0.20 mug L-1 Mn 1.1 mug L-1 Ni. The relatively standard deviations (n = 12) were less than or equal to 3%, less than or equal to 6%, less than or equal to 2%, less than or equal to 3.4%, less than or equal to 1.3%, and less than or equal to 2% for Al, As, Cu, Fe, Mn, and Ni, respectively, the recoveries of Al, As, Cu, Fe, Mn and Ni added to fuel ethanol samples varied from 77% to 112%, 92% to 114%, 104% to 113%, 73% to 116%, 91% to 122% and 93% to 116%, respectively. Accuracy was checked for Al, As, Cu, Fe, Mn, and Ni determination in 20 samples purchased at local gas stations in Araraquara city, Brazil. A paired t-test showed that the results were in agreement at the 95% confidence level with those obtained by single-element GFAAS.

Direct determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by simultaneous GFAAS using integrated platforms pretreated with W-Rh permanent modifier together with Pd plus Mg modifier

A method is proposed for the simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by electrothermal atomic absorption spectrometry (ETAAS) using W-Rh permanent modifier together with Pd(NO3)(2) + Mg(NO3)(2) conventional modifier. The integrated platform of a transversely heated graphite atomizer (THGA) was treated with tungsten, followed by rhodium, forming a deposit containing 250 mug W + 200 mug Rh. A 500-muL, volume of fuel ethanol was diluted with 500 muL, of 0.14 mol L-1 HNO3 in an autosampler cup of the spectrometer. Then, 20 muL, of the diluted ethanol was introduced into the pretreated graphite platform followed by the introduction of 5 mug Pd(NO3)(2) + 3 mug Mg(NO3)(2). The injection of this modifier was required to improve arsenic and iron recoveries in fuel ethanol. Calibrations were carried out using multi-element reference solutions prepared in diluted ethanol (1 + 1, v/v) acidified to 0. 14 mol L-1 HNO3. The pyrolysis and atomization temperatures of the heating program were 1200degreesC and 2200degreesC, respectively, which were obtained with multielement reference solutions in acidic diluted ethanol (1 + 1, v/v; 0. 14 mol L-1 HNO3). The characteristic masses for the simultaneous determination in ethanol fuel were 78 pg Al, 33 pg As, 10 pg Cu, 14 pg Fe, 7 pg Mn, and 24 pg Ni. The lifetime of the pretreated tube was about 700 firings. The detection limits (D.L.) were 1.9 mug L-1 Al, 2.9 mug L-1 As, 0.57 mug L-1.Cu, 1.3 mug L-1 Fe, 0.40 mug L-1 Mn, and 1.3 mug L-1 Ni. The relative standard deviations (n = 12) were 4%, 4%, 3%, 1.5%, 1.2%, and 2.2% for Al, As, Cu, Fe, Mn, and Ni, respectively. The recoveries of Al, As, Cu, Fe, Mn, and Ni added to the fuel ethanol samples varied from 81% to 95%, 80% to 98%, 97% to 109%, 85% to 107%, 98% to 106% and 97% to 103%, respectively. Accuracy was checked for the Al, As, Cu, Fe, Mn, and Ni determination in 10 samples purchased at a local gas station in Araraquara-SP City, Brazil. A paired t-test showed that at the 95% confidence level the results were in agreement with those obtained by single-element ETAAS.

Determinação direta e simultânea de 'AL', 'AS', 'CU', 'FE', 'MN' e 'NI' em álcool etílico hidratado combustível por espectrometria de absorção atômica em forno de grafite

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

Evaluation of diffusive gradients in thin films technique (DGT) for measuring Al, Cd, Co, Cu, Mn, Ni, and Zn in Amazonian rivers

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

Catalytic reduction of NO, by CO on hydrotalcites-derived mixed oxides CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu)

Two series of mixed oxides, CoAlM and MgAlM (M = Cr, Mn, Fe, Co, Ni, Cu), were prepared by calcining their corresponding hydrotalcite-like compounds (HTLc). The ratio of Mg: Al: M (or Co: Al: hi) was 3:1:1. The catalytic activity of all samples for the reaction of NO + CO was investigated. The results showed that the activity of CoAlM was much higher than that of MgAlM. The structure and the property of redox were characterized by XRD and H-2-TPR. The results indicated that only MgO phase was observed after calcining MgAlM hydrotalcites, and the transition metals became more stable. The spinel-like phase appeared in all of CoAlM samples after the calcination, and the transition metals were changed to be more active, and easily reduced. The activities of three series of mixed oxides CoAlCu obtained from different preparation methods, different ratio of Co:Al: Cu and at different calcination temperatures, were studied in detail for proposing the mechanism of reaction. The ability of adsorption of NO and CO were investigated respectively for supporting the mechanism.

Efeito de adições de Ni e Mg sobre o comportamento térmico, mecânico e elétrico de ligas Al-Cu-Fe solidificadas unidirecionalmente

Este trabalho estudou a influência dos teores dos solutos Mg e Ni na modificação das propriedades térmicas, elétricas e mecânicas de uma liga Al-Cu-Fe para aplicação como condutor de energia elétrica. Para a realização do presente estudo, as ligas foram obtidas por fundição unidirecional horizontal, a partir da base do alumínio de pureza comercial com adição dos teores 0,05%p Cu e [0,24 a 0,28]%p Fe. Tal base foi modificada em uma primeira etapa com teores de 0,45, 0,60 e 0,80%p Mg. As ligas obtidas com estes teores tiveram suas propriedades estudadas para que se selecionasse um teor de Mg para posterior adição de Ni à liga. O estudo destas propriedades na primeira etapa passou pela análise das propriedades térmicas: velocidade de solidificação (V_L) e taxa de resfriamento (Ṫ). A caracterização elétrica estudou a propriedade condutividade elétrica (φ) e o levantamento das propriedades mecânicas: limite de resistência à tração (σ) e microdureza Vickers (HV). A liga com adição de Ni passou por tratamentos térmicos de envelhecimento, por 1, 4 e 8h. Estas amostras foram analisadas em um microscópio eletrônico de varredura - MEV pelos sinais de elétrons retroespalhados – ERE e espectroscopia de energia dispersiva – EDS. Como resultados do estudo, encontrou-se que adições de Mg influenciaram significativamente a viscosidade das ligas, elevando as velocidades de solidificação nos instantes finais. Os ensaios de microdureza das amostras envelhecidas mostraram que houve um acréscimo significativo de dureza na quarta hora de envelhecimento, da mesma forma que as análises de EDS mostraram que a concentração de Ni também elevou-se nesta condição de tratamento.

Bainitic precipitation in the Cu-9 wt.%Al-4 wt.%Mn-5 wt.%Ag alloy

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

Strength-ductility behaviour of Al-Si-Cu-Mg casting alloys in T6 temper

A comparative study of the mechanical properties of 20 experimental alloys has been carried out. The effect of different contents of Si, Cu, Mg, Fe and Mn, as well as solidification rate, has been assessed using a strength-ductility chart and a quality index-strength chart developed for the alloys. The charts show that the strength generally increases and the ductility decreases with an increasing content of Cu and Mg. Increased Fe (at Fe/Mn ratio 0.5) dramatically lowers the ductility and strength of low Si alloys. Increased Si content generally increases the strength and the ductility. The increase in ductility with increased Si is particularly significant when the Fe content is high. The charts are used to show that the cracking of second phase particles imposes a limit to the maximum achievable strength by limiting the ductility of strong alloys. The (Cu + Mg) content (at.%), which determines the precipitation strengthening and the volume fraction of Cu-rich and Mg-rich intermetallics, can be used to select the alloys for given strength and ductility, provided the Fe content stays below the Si-dependent critical level for the formation of pre-eutectic alpha-phase particles or beta-phase plates.