Sugars Electrooxidation at Glassy Carbon Electrode Decorate with Multi-Walled Carbon Nanotubes with Nickel Oxy-Hydroxide

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

Electrocatalytic oxidation of urea by nanostructured nickel/cobalt hydroxide electrodes

The present paper describes the catalytic oxidation of urea performed by nickel hydroxide and nickel/cobalt hydroxide modified electrodes by using both electrodeposited films and nanoparticles. The incorporation of Co foreign atoms leads to a slight increase in sensitivity besides the shift in redox process, avoiding the oxygen reaction. Nanostructured Ni80Co20(OH)(2) was synthesized by sonochemical route producing 5 nm diameter particles characterized by high-resolution transmission electron microscopy (HRTEM) being immobilized onto electrode by using the electrostatic Layer-by-layer technique, yielding attractive modified electrodes for sensor development. (C) 2007 Elsevier Ltd. All rights reserved.

Determination of Glycerol in Biodiesel Using a Nickel(II) Oxyhydroxide Chemically Modified Electrode by Cyclic Voltammetry

A glassy carbon electrode chemically modified with nickel oxyhydroxide from a nickel hexacyanoferrate (NiHCF) film was used to determine glycerol in biodiesel by cyclic voltammetry. The modified electrode exhibited a linear response to glycerol concentration in the range from 0.05 to 0.35mmol L-1, and a detection limit of 0.030mmol L-1. The glycerol concentration found in the biodiesel sample was 0.156mmol L-1. The method developed in this study showed a recovery of (100.3±5.0)%. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and characterization of alpha-nickel (II) hydroxide particles on organic-inorganic matrix and its application in a sensitive electrochemical sensor for vitamin D determination

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

Geochemistry of Mid-Atlantic Ridge sediments

Geochemical compositions and Sr and Nd isotopes were measured in two cores collected ~2 and 5 km from the Rainbow hydrothermal vent site on the Mid-Atlantic Ridge. Overall, the cores record enrichments in Fe and other metals from hydrothermal fallout, but sequential dissolution of the sediments allows discrimination between a leach phase (easily leachable) and a residue phase (refractory). The oxy-anion and transition metal distribution combined with rare earth element (REE) patterns suggest that (1) the leach fraction is a mixture of biogenic carbonate and hydrothermal Fe-Mn oxy-hydroxide with no significant contribution from detrital material and (2) >99.5% of the REE content of the leach fraction is of seawater origin. In addition, the leach fraction has an average 87Sr/86Sr ratio indistinguishable from modern seawater at 0.70916. Although we lack the epsilon-Nd value of present-day deep water at the Rainbow vent site, we believe that the REE budget of the leach fraction is predominantly of seawater origin. We suggest therefore that the leach fraction provides a record of local seawater epsilon-Nd values. Nd isotope data from these cores span the period of 4-14 ka (14C ages) and yield epsilon-Nd values for North East Atlantic Deep Water (NEADW) that are higher (-9.3 to -11.1) than those observed in the nearby Madeira Abyssal Plain from the same depth (-12.4 ± 0.9). This observation suggests that either the Iceland-Scotland Overflow Water (ISOW) and Lower Deep Water contributions to the formation of NEADW are higher along the Mid-Atlantic Ridge than in the surrounding basins or that the relative proportion of ISOW was higher during this period than is observed today. This study indicates that hydrothermal sediments have the potential to provide a higher-resolution record of deep water epsilon-Nd values, and hence deepwater circulation patterns in the oceans, than is possible from other types of sediments.

Investigation into the potential for establishing a self-sustainable wetland ecosystem over pyritic mine tailings

Research was conducted to investigate the potential for ecologically engineering a sustainable wetland ecosystem over pyritic mine tailings to prevent the generation of acid mine drainage. Ecological engineering is technology with the primary goal being the creation of self-sustainable ecological systems. Work involved the design and construction of a pilot-scale wetland system comprising three wetland cells, each covering 100 m2. Approximately forty tonnes of pyritic mine tailings were deposited on the base of the first cell above a synthetic liner, covered with peat, flooded and planted with emergent wetland macrophytes Typha latifolia, Phragmites australis, and Juncus effusus. The second cell was constructed as a conventional free water surface wetland, planted identically, and used as a reference wetland/experimental control. Wetland monitoring to determine long-term sustainability focused on indicators of ecosystem health including ecological, hydrological, physico-chemical, geochemical, and biotic metrics. An integrated assessment was conducted that involved field ecology in addition to ecological risk assessment. The objective of the field ecology study was to use vegetative parameters as ecological indicators for documenting wetlands success or degradation. The goal of the risk assessment was to determine if heavy-metal contamination of the wetland sediments occurred through metal mobilisation from the underlying tailings, and to evaluate if subsequent water column chemistry and biotic metal concentrations were significantly correlated with adverse wetland ecosystem impacts. Data were used to assess heavy metal bioavailability within the system as a function of metal speciation in the wetland sediments. Results indicate hydrology is the most important variable in the design and establishment of the tailings wetland and suggest a wetland cover is an ecologically viable alternative for pyritic tailings which are feasible to flood. Ecological data indicate that in terms of species richness and diversity, the tailings-wetland was exhibiting the ecological characteristics of natural wetlands within two years. Ata indicate that pH and conductivity in the tailings-wetland were not adversely impacted by the acid-generating potential or sulphate concentration of the tailings substrate and its porewater. Similarly, no enhanced seasonal impacts from sulphate or metals in the water column, nor adverse impacts on the final water quality of the outflows, were detected. Mean total metal concentrations in the sediments of the tailings-wetland indicate no significant adverse mobilisation of metals into the peat substrate from the tailings. Correlation analyses indicate a general increase in sediment metal concentration in this wetland with increasing water depth and pH, and a corresponding decrease in the metal concentrations of the water column. Sediment extractions also showed enrichment of Cd, Fe, Pb and Zn in the oxidisable fraction (including sulphides and organic matter) of the tailings-wetland sediments. These data suggest that adsorption and coprecipitation of metals is occurring from the water column of the tailings wetland with organic material at increasing depths under reducing conditions. The long-term control of metal bioavailability in the tailings wetland will likely be related to the presence and continual build-up of organic carbon binding sites in the developing wetland above the tailings. Metal speciation including free-metal ion concentration and the impact of physico-chemical parameters particularly pH and organic matter, were investigated to assess ecotoxicological risk. Results indicate that potentially bioavailable metals (the sum of the exchangeable and reducible fractions) within the tailings wetland are similar to values cited for natural wetlands. Estimated free-metal ion concentrations calculated from geochemical regression models indicate lower free-metal ion concentrations of Cd in the tailings wetland than natural wetlands and slightly higher free-metal ion concentrations of Pb and Zn. Increased concentrations of metals in roots, rhizomes and stems of emergent macrophytes did not occur in the tailings wetland. Even though a substantial number of Typha latifolia plants were found rooting directly into tailings, elevated metals were not found in these plant tissues. Phragmites also did not exhibit elevated metal concentrations in any plant tissues. Typha and Phragmites populations appear to be exhibiting metal-tolerant behaviour. The chemistry of the water column and sediments in Silvermines wetland were also investigated and were much more indicative of a wetland system impacted by heavy metal contamination than the tailings-wetland. Mean Dc, Fe, Mn, Pb and Zn concentrations in the water column and sediments of Silvermines wetlands were substantially higher than in the pilot wetlands and closely approximate concentrations in these matrices contaminated with metals from mining. In addition, mean sulphate concentration in Silvermines wetland was substantially higher and is closer to sulphate concentrations in waters associated with mining. Potentially bioavailable metals were substantially elevated in Silvermines wetland in comparison to the pilot wetlands and higher than those calculated for natural rive sediments. However, Fe oxy-hydroxide concentrations in Silvermines sediments are also much higher than in the pilot wetlands and this significantly impacts the concentration of free-metal ions in the sediment porewater. The free-metal ion concentrations for Pb and Zn indicate that Silvermines wetland is retaining metals and acting as a treatment wetland for drainage emanating from Silvermines tailings dam.

Caracterização e propriedades do material coloidal nanoestruturado β-FeOOH/bentonita

A new mixed material was obtained through the combination of the suspensions of iron oxy-hydroxide and bentonite clay, denoted BFe. Analysis of its structure (XRD, Mossbauer and TGA) and composition (AAS) suggests the maintenance of the layer structure of the clay and an increase in the thermal stability of the BFe. Electrochemical studies performed in different electrolytes show that only in an alkaline medium it is possible to observe the redox peaks relative to the processes involving Fe+2/Fe+3 pair. Tests that evaluated the potential use of the photo-Fenton process showed an efficient degradation process of the dyes in significantly reduced reaction times.

Reindustrialização de resíduos galvânicos como matérias-primas para esmaltes cerâmicos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Fotocromismo e luminescência de compostos a base de tungstênio e íons terras raras trivalentes via síntese hidrotérmica

Pós-graduação em Química - IQ

Desenvolvimento de detector eletroquímico para cromatografia líquida de alta eficiência baseado em um eletrodo modificado com nanopartículas metálicas para determinação de ácidos carboxílicos em vinhaça de cana-de-açúcar

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

Determinação de açucares em bagaço de palha de cana-de-açúcar por cromatografia líquida de alta eficiência com detecção eletroquímica utilizando eletrodos de nanotubos modificados com óxidos metálicos

Pós-graduação em Química - IQ

Raman and XRD study on brookite-anatase coexistence in cathodic electrosynthesized titania

Among the many methods developed for the synthesis of titanium dioxide, cathodic electrosynthesis has not received much attention because the resulting amorphous oxy-hydroxide matrix demands a further thermal annealing step to be transformed into crystalline titania. However, the possibility of filling deep recessed templates by the control of the solidliquid interface makes it a potentially suitable technique for the fabrication of porous scaffolds for photovoltaics and photocatalysis. Furthermore, a careful control of the crystallization process enables the growth of larger grains with lower density of grain boundaries, which act as electron traps that slow down electronic transport and promote charge recombination. In this report, well crystallized titania deposits were obtained by thermal annealing of amorphous deposits fabricated by cathodically assisted electrosynthesis on indium-tin oxide (ITO)substrates. The combined use of Raman spectroscopy and X-ray diffraction showed that the crystallization process is more intricate than previously assumed. It is shown that the amorphous matrix evolves into a rutile-free mixture of brookite and anatase at temperatures as low as 200 degrees C that persists up to 800 degrees C, when pure anatase dominates. The amount of brookite in the brookiteanatase mixture reaches a maximum at 400 degrees C. This very simple method for obtaining a brookiteanatase mixture and the ability to tune their proportions by thermal annealing is a promising alternative whose potential for solar cells and photocatalysis deserves a careful evaluation. Copyright (C) 2011 John Wiley & Sons, Ltd.

Geochemistry of sediment cores from the Rainbow vent site

A geochemical investigation was carried out on two sediment cores collected at 2 and 5 km from the Rainbow hydrothermal vent site. Bulk sediment compositions indicate that these cores record clear enrichments in Fe, Cu, Mn, V, P and As from hydrothermal plume fallout (Cave et al., 2002, doi:10.1016/S0016-7037(02)00823-2). Sequential dissolution of the bulk sediments has been used to discriminate between a leach (biogenic and oxy-hydroxide) component and a residual phase (detrital and sulphide/sulphate fractions). Major element data (Al, Fe, Ti, Mn, Mg, Ca, Si and index%) reveal that the hydrothermal input, as recorded in the leach phase, is much stronger than apparent from bulk sediment analyses alone. REE patterns for the leach phase record contributions from both biogenic carbonate (mimicking seawater REE patterns) and hydrothermal oxy-hydroxides, with the latter exhibiting positive Eu anomalies (hydrothermal derived) and negative Ce anomalies (seawater derived). Based on major element and REE data, the residue contains contributions from aeolian dust input, local MORB material and a hydrothermal component. Ternary REE mixing calculations indicate that most of the REE within the residual fraction (~80%) is derived from hydrothermal material, while detrital contributions to the REE budget, as deep-sea clay and volcanic debris, are <20%. By combining bulk and REE data for the various end-member components of the residue, we calculate that the chemical composition of the residue hydrothermal end-member is high in Ca (6-15%) and with a Nd/Sr ratio of 0.004. These characteristics indicate the presence of low-solubility hydrothermal sulphate (rather than sulphide) material within the residue component of Rainbow hydrothermal sediments.

Annotated record of the detailed examination of ferromanganese concretions from the Gulf of Bothnia in the Baltic Sea

Ferromanganese concretions cover large areas of the Gulf of Bothnia. They are flat to well-rounded, the rounded ones being richer in oxyhydroxides of iron and manganese. Rounded and ellipsoidal nodules, particularly those in the northern Gulf of Bothnia, are richest in Mn, Ni, Ba and Cu, which probably coexist in a Mn oxyhydroxide phase. Flat nodules are enriched in Fe, P, rare earths and As, probably associated with an Fe oxy-hydroxide component. Aluminum, V, Cr and Ti occur in still another phase. The sediments of the gulf generally consist of a 10-50 mm-thick layer of oxidized surface sediment, enriched in Mn, Ba, P and Ni lying on top of reduced sediments which are diagenetically depleted in these elements. The remobilized elements have redeposited in the nodules, but this process cannot explain the origin of all the nodular material. Some released Mn, Ba and Ni furthermore enter into suspended phases, which eventually leave the Baltic Sea. The economic value of the nodules in the Gulf of Bothnia is probably limited at present.

(Table 1) Mn, Fe, TOC and CaCO3 concentrations in bottom sediments and silt waters of Kandalaksha Bay, White Sea

The redox stratification of bottom sediments in Kandalaksha Bay, White Sea, is characterized by elevated concentrations of Mn (3-5%) and Fe (7.5%) in the uppermost layer, which is two orders of magnitude and one and a half times, respectively, higher than the average concentrations of these elements in the Earth's crust. The high concentrations of organic matter (Corg = 1-2%) in these sediments cannot maintain (because of its low reaction activity) the sulfate-reducing process (the concentration of sulfide Fe is no higher than 0.6%). The clearest manifestation of diagenesis is the extremely high Mn2+ concentration in the silt water (>500 µM), which causes its flux into the bottom water, oxidation in contact with oxygen, and the synthesis of MnO2 oxy-hydroxide enriching the surface layer of the sediments. Such migrations are much less typical of Fe. Upon oxygen exhaustion in the uppermost layer of the sediments, the synthesized oxyhydroxides (MnO2 and FeOOH) serve as oxidizers of organic matter during anaerobic diagenesis. The calculated diffusion-driven Mn flux from the sediments (280 µM/m**2 day) and corresponding amount of forming Mn oxyhydrate as compared to opposite oxygen flux to sediments (1-10 mM/m**2 day) indicates that >10% organic matter in the surface layer of the sediments can be oxidized with the participation of MnO2. The roles of other oxidizers of organic matter (FeOOH and SO4**2-) becomes discernible at deeper levels of the sediments. The detailed calculation of the balance of reducing processes testifies to the higher consumption of organic matter during the diagenesis of surface sediments than it follows from the direct determination of Corg. The most active diagenetic redox processes terminate at depths of 25-50 cm. Layers enriched in Mn at deeper levels are metastable relicts of its surface accumulation and are prone to gradual dissemination.