Synthesis of lanthanide oxysulfides activated by Eu3+. A topochemical reaction

The oxysulfide compounds La2O2S:Eu and Y2O2S were obtained directly from thermodecomposition of the respective oxalate compounds under argon and sulfur vapor, the obtained compounds were analyzed by infrared spectroscopy, X ray diffraction and luminescence spectroscopy. The particle size distribution and crystalline habit of the compounds were observed by scanning electron microscopy. Although the particle size of the oxysulfide was found to be 30%-40% smaller than the precursor oxalates, the initial morphology was completely maintained, which indicates the occurrence of a topochemical reaction from oxalates to oxysulfides. © Gauthier-Villars.

Preparation and characterization of uniform, spherical particles of Y2O2S and Y2O2S:Eu

The preparation of spherical Y2O2S and Y2O2S:Eu particles using a solid-gas reaction of monodispersed precursors with elemental sulfur vapor under an argon atmosphere has been investigated. The precursors, undoped and doped yttrium basic carbonates, are synthesized by aging a stock solution containing the respective cation chloride and urea at 82-84 °C. Y2O2S and Y2O2S:Eu were characterized in terms of their composition, crystallinity and morphology by chemical analysis, X-ray powder diffraction (XRD), IR spectroscopy, and scanning electron microscopy (SEM). The Eu-doped oxysulfide was also characterized by atomic absorption spectrophotometry and luminescence spectroscopy. The spherical morphology of oxysulfide products and of basic carbonate precursors suggests a topotatic inter-relationship between both compounds.

Crystallographic and spectroscopic studies on palladium(II) complexes containing pyrazole and thiocyanate ligands

Mononuclear palladium(II) complexes containing both pyrazole-type ligands and thiocyanate, of general formula [Pd(SCN) 2(L) 2] {L = pyrazole (HPz) and l-phenyl-3-methylpyrazole (phmPz)} have been prepared and characterized by elemental analysis, i.r. and n.m.r. spectroscopy and by single crystal X-ray diffraction methods. The Pd atom in these structures lies on the crystallographic inversion center; in a square-planar coordination geometry made by two sulfur and two nitrogen atoms of the ligands, both in trans positions.

Characterization of bornite (Cu5FeS4) electrodes in the presence of the bacterium Acidithiobacillus ferrooxidans

Bornite electrodes were characterized in the absence or in the presence of Acidithiobacillus ferrooxidans, which is an important microorganism involved in metal bioleaching processes. The presence of the bacterium modified the mineral/electrolyte interface, increasing the corrosion rate, as revealed by interferometric, AEM, ICP and EIS analyses. As a consequence of bacterial activity the electrode became porous, increasing its surface heterogeneity. This behavior was correlated with the evolution of impedance diagrams obtained during the time course of experiments. The main difference in these diagrams was the presence of an inductive feature (up to 44 h), which was related to bacterial action on the mineral dissolution, better than to its adhesion on the bornite. The total real impedance measured in presence of the bacterium was about 10 times lower than in its absence, due to the acceleration of the mineral dissolution, because an oxidant environment was maintained.

Assessment of anaerobic sewage sludge quality for agricultural application after metal bioleaching

The effects of metal bioleaching on nutrient solubilization, especially nitrogen and phosphorous, from anaerobically-digested sewage sludge were investigated in this work. The assessment of the sanitary quality of the anaerobic sludge after bioleaching was also carried out by enumerating indicator (total coliforms, fecal coliforms, and fecal streptococci) and total heterotrophic bacteria. The experiments of bioleaching were performed using indigenous sulphur-oxidizing bacteria (Thiobacillus spp.) as inoculum and samples of anaerobically-digested sludge. Nitrogen and phosphorous solubilization from sewage sludge was assessed by measuring, respectively, the concentration of Total Kjeldahl Nitrogen, ammonia, nitrate/nitrite, and soluble and total phosphorous before and after the bioleaching assays. At the end of the experiment, after 4 days of incubation (final pH of 1.4), the following metal solubilization yields were obtained: zinc, 91%; nickel, 87%; copper, 79%; lead, 52%; and chromium, 42%. As a result of sludge acidification, the viable counts of selected indicator bacteria were decreased to below the detection limit (4 × 103 cfu 100 ml-1), followed by an increase in the mineral fraction of nitrogen (from 6 to 10%) and in the soluble fraction of phosphorous (from 15 to 30%). Although some loss of sludge nutrients can occur during solid-liquid separation following bioleaching, its beneficial effects as metal removal and reduction of pathogenic bacteria are sufficient to consider the potential of this treatment before sludge disposal onto agricultural fields.

Metano entérico de bovinos leiteiros em condições tropicais brasileiras

The objective of this work was to quantify methane (CH4) emission using the sulfur hexafluoride (SF6) tracer technique, by dairy cattle on pasture in Brazilian tropical field conditions. Measurements were performed in the rainy season, with Holstein and Holstein x Zebu crossbred, from lactating and dry cows and heifers grazing fertilized Tobiatã grass, and heifers grazing unfertilized Brachiaria grass. Methane and SF6 concentrations were determined by gas chromatograph. Methane emissions by lactating cows varied from 13.8 to 16.8 g/hour, by dry cows from 11.6 to 12.3 g/hour, by heifers grazing fertilized grass was 9.5 g/hour and by heifers grazing unfertilized grass varied from 7.6 to 8.3 g/hour or 66 to 72 kg/head/year. Methane emission per digestive dry matter intake (DMDI) varied from 42 to 69 g/kg DMDI for lactating cows, 46 to 56 g/kg for dry cows, 45 to 58 g/kg for heifers grazing fertilized grass and 58 to 62 g/kg for heifers in unfertilized grass pasture. The CH4 emission measured on dairy cattle feeding tropical grasses was higher than that observed for temperate climate conditions.

Retorno de nutrientes ao solo via deposição de serapilheira de quatro espécies leguminosas arbóreas na região de Botucatu - São Paulo, Brasil

The annual litter fall production and the concentrations of macronutrients of four leguminous tree species were evaluated. The experiment was installed in a distrophic red yellow latosol (Oxisol), derivative of the Bauru sandstone group. The studied species were: Leucaena leucocephala. Acacia melanoxylon, L. diversifolia and Mimosa scabrella. The experimental design was randomized blocks, with four treatments (species) and four replications. The litter fall was collected in boxes measuring 50×50×10 cm, two boxes by treatment in each block. The material was collected monthly and dried, weighed and chemically analyzed. The litter fall deposition occurred in the following order: M. scabrella (7,051 kg ha -1 ano -1), A. melanoxylon (2,789 kg ha -1 ano -1), L. diversifolia (1,576 kg ha -1 ano -1) and L. leucocephala (1,389 kg ha -1 ano -1). The content of nutrients obeyed the following order: N>Ca>K>Mg>P>S, with the exception of L. leucocephala that presented a bigger content of S in relation to the P.

Determination of vanadium in urine by electrothermal atomic absorption spectrometry using hot injection and preconcentration into the graphite tube

In this work it was developed a procedure for the determination of vanadium in urine samples by electrothermal atomic absorption spectrometry using successive injections for preconcentration into a preheated graphite tube. Three 60 μL volumes were sequentially injected into the atomizer preheated to a temperature of 110°C. Drying and pyrolysis steps were carried out after each injection. A chemical modifier, barium difluoride (100 mg L-1), and a surfactant, Triton X-100 (0.3% v v-1), were added to the urine sample. When injecting into a hot graphite tube, the sample flow-rate was 0.5 μL s-1. The limits of detection and quantification were 0.54 and 1.82 without preconcentration, and 0.11 and 0.37 μg L-1 with preconcentration, respectively. The accuracy of the procedure was evaluated by an addition-recovery experiment employing urine samples. Recoveries varied from 96.0 to 103% for additions ranging from 0.8 to 3.5 μg L-1 V. The developed procedure allows the determination of vanadium in urine without any sample pretreatment and with minimal dilution of the sample.

Lipoic acid and ascorbic acid affect plasma free amino acids selectively in the teleost fish pacu (Piaractus mesopotamicus)

Most studies on the antioxidants, lipoic acid (LA) and ascorbic acid (AA), focused on species that, unlike teleost fish, are not scurvy-prone, and are able to synthesize AA. The antioxidant properties of LA may make it useful in aquaculture nutrition, but several effects must first be investigated, and we address here plasma free amino acids (FAA). In mammals, LA and AA in high doses were claimed to alter plasma FAA profile; to our knowledge, however, no data are available in fish. We therefore studied the effects of dietary LA and AA on plasma FAA in the South American teleost fish pacu, which is being used increasingly in aquaculture. LA treatment decreased concentrations of 18 of 23 individual FAA; specifically, dispensable and total FAA were significantly affected. Ornithine was elevated (+26%) in LA-treated fish and significantly decreased ratios of plasma [Arg]/[Orn] and other individual [FAA]/[Orn] were observed. LA and AA both affected sulfur FAA concentrations. Plasma cystine levels were significantly increased in the LA-supplemented groups. AA had little effect on most amino acids, and no interaction with LA was detected. AA supplementation did, however, significantly lower taurine (-42%) and cystathionine (-31%) levels in plasma. No effect on the branched chain:aromatic amino acid ratios was observed. The data indicate that at the dietary level studied, LA and AA independently affect selected plasma FAA in pacu, and suggest that any use of LA in particular as a dietary supplement should take into account an altered plasma FAA profile.

Synthesis, characterization, and biological activity of a new palladium(II) complex with deoxyalliin

Synthesis, characterization, and biological activity of a new water-soluble Pd(II)-deoxyalliin (S-allyl-L-cysteine) complex are described in this article. Elemental and thermal analysis for the complex are consistent with the formula [Pd(C6H10NO2S)2]. 13C NMR, 1H NMR, and IR spectroscopy show coordination of the ligand to Pd(II) through S and N atoms in a square planar geometry. Final residue of the thermal treatment was identified as a mixture of PdO and metallic Pd. Antiproliferative assays using aqueous solutions of the complex against HeLa and TM5 tumor cells showed a pronounced activity of the complex even at low concentrations. After incubation for 24 h, the complex induced cytotoxic effect over HeLa cells when used at concentrations higher than 0.40 mmol/L. At lower concentrations, the complex was nontoxic, indicating its action is probably due to cell cycle arrest, rather than cell death. In agreement with these results, the flow cytometric analysis indicated that after incubation for 24 h at low concentrations of the complex cells are arrested in G0/G1. © 2005 NRC Canada.

Corrosion protection of fluorzirconate glasses coated by a layer of surface modified tin oxide nanoparticles

The protection efficiency against water corrosion of fluorozirconate glass, ZBLAN, dip-coated by nanocrystalline tin oxide film containing the organic molecule Tiron® was investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The chemical bonding structure of the surface region and morphology were studied before and after two water exposure periods of 5 and 30 min. The results of the analysis for the as-grown sample revealed a SnO1.6 phase containing carbon and sulfur, related to Tiron®, and traces of elements related to ZBLAN (Zr, F, Ba). This fact and the clear evidence of the presence of tin oxifluoride specie (SnOxF y) indicates a diffusion of the glass components into the porous coating. After water exposure, the increase of the oxygen concentration accompanied by a strong increase of Zr, F, Ba and Na content is interpreted as filling of the nanopores of the film by glass compounds. The formation of a compact protective layer is supported by the morphological changes observed by AFM. © 2005 Elsevier B.V. All rights reserved.

Patulina: Incidência e controle em derivados de maçã

The patulin, (4hydroxy-4furo[3,2-c]pyran(6H)-1), is a thermal resistent mycotoxin produced by several species of fungi are common in plants, mainly in derivatives and apples. Studies on the toxicity in animals have shown that mycotoxin has character teratogenic, and carcinogenic in mice immunotoxic. Its biosynthesis is well understood involving a series of reactions of condensation and oxiredução, many catalyzed by enzymes. The danger of contamination of food with patulin, warning about the need for a more rigorous control. Recent research aimed their removal and degradation as well as increase the sensitivity of the tests, making them faster and at less cost. The removal of patulin of food is made with composite adsorbents, with inconvenience to diminish the quality of the product by adsorbs other components desirable. The degradation is made with sulfur compounds, which are not allowed in food in many countries, and the growth of yeasts, such as the production of cider. Many yeasts have resistance against patulin and produce compounds capable degrade it. Here, we reviewed research on patulin with emphasis on its influence in food industry, incidence of patulin in apple juice and other foods, maximum permissible concentrations, health effects, biosynthesis, removal, degradation and most widely used methods for its detection and quantification.

Indoor air quality assessment of elementary schools in Curitiba, Brazil

The promotion of good indoor air quality in schools is of particular public concern for two main reasons: (1) school-age children spend at least 30% of their time inside classrooms and (2) indoor air quality in urban areas is substantially influenced by the outdoor pollutants, exposing tenants to potentially toxic substances. Two schools in Curitiba, Brazil, were selected to characterize the gaseous compounds indoor and outdoor of the classrooms. The concentrations of benzene, toluene, ethylbenzene, and the isomers xylenes (BTEX); NO2; SO2; O3; acetic acid (HAc); and formic acid (HFor) were assessed using passive diffusion tubes. BTEX were analyzed by gas chromatography-ion trap mass spectrometry and other collected gasses by ion chromatography. The concentration of NO2 varied between 9.5 and 23 μg m-3, whereas SO2 showed an interval from 0.1 to 4.8 μg m-3. Within the schools, BTEX concentrations were predominant. Formic and acetic acids inside the classrooms revealed intermediate concentrations of 1.5 μg m-3 and 1.2 μg m-3, respectively. © Springer Science + Business Media B.V. 2009.

Utilização do coque verde de petróleo da Petrobras em substituição parcial ao carvão mineral das misturas injetadas em altos fornos

The Petrobras produced green petroleum coke (GPC) is a carbon rich fuel, virtually ash-free, with low sulfur content, and is a fuel suitable to replace metallurgical coke in blast furnaces. The GPC was tested in a pulverized coal injection simulator built in the Volta Redonda research center. It presented a low burning efficiency due to low volatile material content and high substitution rate by the carbon content. The tests were carried out in blast furnaces with ≤ 50% Petrobras GPC in the coal blends. The injected coal/CVP mixtures produced no negative side effects in the blast furnace grinding systems, pneumatic conveying, or operating process. The mixture burning process inside the blast furnace showed a decrease in fuel consumption, with a significant reduction in metallurgical coke consumption. The industrial-scale tests of the GPC mixtures did not reach the 70% maximum for lack of the GPC feedstock, which is necessary to continue with standard coal mixtures.

Leaf spray fertilization of boron and zinc on productivity and fruit quality of Japanese pear tree

The cultivation of fruit plants from temperate climate in tropical or subtropical regions can be a good income alternative for the producer. However, due to the little existent information about cultivation of those fruit plants, the producers use imported techniques of other producing areas, or even an association of practices used for other fruit plants, pointing out the leaf spray fertilization of micronutrients without appropriate scientific base. In this context, the objective of this study was to verify the effect of the leaf spray fertilization of B and Zn on productivity and fruit quality of Japanese pear tree. The experiment was conducted from 2004 to 2005, in Ilha Solteira, in northwestern São Paulo State-Brazil. The climate is, according to the Köpppen Classification, tropical wet and dry (Aw). The 'Okusankichi' cultivar, grafted on Pyrus communis L. rootstock was used as well as doses of 110 g.ha-1 of B and 250 g.ha-1 of Zn in each application. The treatments were: T1. water, T2. boric acid, T3. zinc sulfate, T4. T2 + T3, T5. boric acid + urea + citric acid + EDTA, T6. zinc sulfate + urea + citric acid + EDTA, T7. T5 + T6, T8. boric acid + urea + citric acid + EDTA + sodium molibdate + sulfur + calcium chloride, T9. zinc sulfate + urea + citric acid + EDTA + Fe sulfate + Mn sulfate + Mg sulfate and, T10. T8+T9. A randomized blocks design was used and the averages were compared by Tukey test. In the first crop the mixture of boric acid with quelating agents were efficient to supply B to the plants and zinc sulfate plus quelating agents were efficient to increase Zn leaf content. However, the productivity and the fruit quality were not influenced by the leaf spray of B and Zn. In the second crop the leaf content of B and Zn and the productivity were not influenced by the leaf spray; the boric acid and the zinc sulfate with or without quelating agents increased the contents of total soluble solids and, the boric acid with or without quelating agents increased the contents of total titratable acidity.