Evaluation of the mixtures ammonium phosphate/magnesium nitrate and palladium nitrate/magnesium nitrate as modifiers for simultaneous determination of Cd, Cr, Ni and Pb in mineral water by GFAAS

A method is described for the simultaneous determination of Cd, Cr, Ni and Pb in mineral water samples by graphite furnace atomic absorption spectrometry with a transversely heated graphite atomizer (THGA) and a longitudinal Zeeman-effect background correction system. The electrothermal behavior of analytes during pyrolysis and atomization steps was studied without modifier, in presence of 5 μg Pd and 3 μg Mg(NO3)2 and in presence of 50 μg NH4H2PO4 and 3 μg Mg(NO3)2. A volume of 20 μL of a 0.028 mol L -1 HNO3 solution containing 50 μg L-1 Ni and Pb, 10 μg L-1 Cr and 5 μg L-1 Cd was dispensed into the graphite tube at 20°C. The mixture palladium/magnesium was selected as the optimum modifier. The pyrolysis and atomization temperatures were fixed at 1000°C and 2300°C, respectively. The characteristic masses were calculated as 2.2 pg Cd, 10 pg Cr, 42 pg Ni and 66 pg Pb and the lifetime of the graphite tube was around 600 firings. Limits of detection based on integrated absorbance were 0.02 μg L-1Cd, 0.94 μg L-1 Cr, 0.45 μg L-1 Ni and 0.75 μg L-1 Pb, which exceeded the requirements of Brazilian Food Regulation that establish the maximum permissible level for Cd, Cr, Ni and Pb at 3 μg L-1, 50 μg L-1, 20 μg L-1 and 10 μg L-1, respectively. The recoveries of Cd, Cr, Ni and Pb added to mineral water samples varied within the 93-108%, 96-104%, 87-101% and 98-108% ranges, respectively. Results of analysis of standard reference materials (National Institute of Standards and Technology: 1640-Trace Elements in Natural Water; 1643d-Trace Elements in Water) were in agreement with certified values at the 95% confidence level.

Structural control of photoluminescence of four poly(urethane-urea-co-1,3,5-triazine)s: Synthesis and characterization

A series of segmented poly(urethane-urea)s containing 1,3,5 triazine in the hard block and hexamethylene spacers in the soft block was prepared. The hard to soft segment ratio was varied systematically, to afford a series of polymers in which the chromophore concentration varied from 4.2% to 18.1%. Although triazine emission is located in the UV region, the films with higher content of the chromophore emitted a visible blue light (425 nm) when excited at the very red-edge of the absorption band. The photophysical properties of the materials were strongly dependent on the relative amount of triazine moieties along the main chain. Isolated moieties emit in copolymers with small amount of triazine groups, indicating that even though in solid state, these moieties tend to be apart. Two photophysical consequences were observed when the amount of triazine increases: there is some energy transfer process involving isolated moieties with consequent decrease of the lifetime and an additional red-edge emission attributed to aggregated lumophores. The mono-exponential decay observed for the isolated form is substituted by a bi-exponential decay of the aggregated species. The materials were not strong emitters, but since the N-containing triazine moieties are good electron transport groups, the polymers have potential application as electron transport enhancers in various applications. © 2006 Elsevier B.V. All rights reserved.

Utilização de nitrato de amônio e de uréia como fontes de nitrogênio na micropropagação de amoreira-preta

The high cost allied to the difficulty in the acquisition of the ammonium nitrate has been taking the accomplishment of works looking for an alternative for the substitution of this source of nitrogen. It was aimed at to study the technical viability of the substitution of the ammonium nitrate for urea, as source of nitrogen in the culture media for the blackberry in vitro cv. Tupy (Rubus sp). Nodal segments were used, already established in vitro, were inoculated in culture media MS and 50% MS, added of 1.0 mg. dm-3 of BAP, solidified with 6 g.dm-3 of agar, pH was adjusted for 5,8 and sterilized to 121 °C and 0,1 MPa for 20 min. The treatments consisted of the substitution of 0; 20; 40; 60; 80 and 100% of NH4NO3 for urea, and the swinging of nitrogen supplied by the culture media MS it was not altered. The explants were maintained by 60 days in growth room with temperature of 27±1 °C, photoperiod of 16 h and luminous intensity of 32 mmol m'2 s'1. The experiment was arranged in a completely randomized design, in factorial (6 x 2) using four repetitions with 16 plants each one. From the obtained results it can be concluded that the urea doesn't substitute NH 4NO3 in the culture media MS as nitrogen source in the culture vitro of blackberry.

The mechanism of dephosphorylation of bis(2,4-dinitrophenyl) phosphate in mixed micelles of cationic surfactants and lauryl hydroxamic acid

(Figure Presented) Mixed micelles of cetyltrimethylammonium bromide (CTABr) or dodecyltrimethylammonium bromide (DTABr) and the α-nucleophile, lauryl hydroxamic acid (LHA) accelerate dephosphorylation of bis(2,4-dinitrophenyl) phosphate (BDNPP) over the pH range 4-10. With a 0.1 mole fraction of LHA in DTABr or CTABr, dephosphorylation of BDNPP is approximately 10 4-fold faster than its spontaneous hydrolysis, and monoanionic LHA - is the reactive species. The results are consistent with a mechanism involving concurrent nucleophilic attack by hydroxamate ion (i) on the aromatic carbon, giving an intermediate that decomposes to undecylamine and 2,4-dinitrophenol, and (ii) at phosphorus, giving an unstable intermediate that undergoes a Lossen rearrangement yielding a series of derivatives including N,N-dialkylurea, undecylamine, undecyl isocyanate, and carbamyl hydroxamate. © 2009 American Chemical Society.

Nodule growth and nitrogen fixation of Calopogonium mucunoides L. show low sensitivity to nitrate

It is well established that nitrate is a potent inhibitor of nodulation and nitrogen fixation in legumes. The objective of this study was to demonstrate the relative insensitivity of these processes to nitrate with Calopogonium mucunoides, a tropical South American perennial legume, native to the cerrado (savannah) region. It was found that nodule number was reduced by about half in the presence of high levels of nitrate (15 mM) but nodule growth (total nodule mass per plant) and nitrogen fixation (acetylene reduction activity and xylem sap ureide levels) were not affected. Other sources of N (ammonium and urea) were also without effect at these concentrations. At even higher concentrations (30 mM), nitrate did promote significant inhibition (ca. 50%) of acetylene reduction activity, but no significant reduction in xylem sap ureides was found. The extraordinary insensitivity of nodulation and N2 fixation of C. mucunoides to nitrate suggests that this species should be useful in studies aimed at elucidating the mechanisms of nitrate inhibition of these processes. © 2010 Springer Science+Business Media B.V.

Fontes e parcelamento do nitrogênio em cobertura, na cultura do milho sob plantio direto

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Produção de rúcula e acúmulo de nitrato em função da adubação nitrogenada

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Composição química e digestibilidade in vitro da massa seca de cana-de-açúcar acrescida de ureia em diferentes tempos de estocagem

The objective of this research was to evaluate the chemical composition and in vitro dry mass (DM) digestibility of sugar cane with urea, maintained in the shade and sun, at different storage times. The utilized design was the completely randomized in a factorial scheme 6x2, that is, six storage times after the mixing (0; 2; 4; 6; 12 and 24 hours) and two storage location (shade and sun), with three replicates. The sugarcane utilized presented 12 months of development and was disintegrated for application of mixture (nine parts of urea for one of ammonium sulfate) to 1.0kg/100.0kg of fresh sugarcane. The samples taken with 12 hours of storage indicated that was an increase in the content of DM and crude protein (CP) of sugar cane compared to the moment of the mixture (307.6 vs. 294.2g/kg of DM and 115.2 vs. 99.3 g/kg of DM, respectively), and the smaller content of neutral detergent fiber (NDF) was observed around of 12 hours of storage (465.0g/kg of DM). The coefficients of in vitro dry mass digestibility (IVDMD) ranged of 0.558 to 0.612 in the times 0 and 12 hours, respectively. The length of storage changes the chemical composition of sugar cane plus urea. The storage location changes the dry mass content and pH values.

Ammonia volatilization losses from surface-applied urea with urease and nitrification inhibitors

Urease inhibitor (UI) and nitrification inhibitor (NI) have the potential to improve N-use efficiency of applied urea and minimize N losses via gaseous emissions of ammonia (NH 3) to the atmosphere and nitrate (NO3-) leaching into surface and ground water bodies. There is a growing interest in the formulations of coating chemical fertilizers with both UI and NI. However, limited information is available on the combined use of UI and NI applied with urea fertilizer. Therefore the aim of this study was to investigate the effects of treating urea with both UI and NI to minimize NH 3 volatilization. Two experiments were set up in volatilization chambers under controlled conditions to examine this process. In the first experiment, UR was treated with the urease inhibitor NBPT [N-(n-butyl) thiophosphoric acid triamide] at a rate of 1060 mg kg -1 urea and/or with the nitrification inhibitor DCD (dicyandiamide) at rates equivalent to 5 or 10% of the urea N. A randomized experimental design with five treatments and five replicates was used: 1) UR, 2) UR + NBPT, 3) UR + DCD 10%, 4) UR + NBPT + DCD 5%, and 5) UR + NBPT + DCD 10%. The fertilizer treatments were applied to the surface of an acidic Red Latosol soil moistened to 60% of the maximum water retention and placed inside volatilization chambers. Controls chambers were added to allow for NH 3 volatilized from unfertilized soil or contained in the air that swept over the soil surface. The second experiment had an additional treatment with surface-applied DCD. The chambers were glass vessels (1.5 L) fit with air inlet and outlet tubings to allow air to pass over the soil. Ammonia volatilized was swept and carried to a flask containing a boric acid solution to trap the gas and then measured daily by titration with a standardized H 2SO 4 solution. Continuous measurements were recorded for 19 and 23 days for the first and second experiment, respectively. The soil samples were then analyzed for UR-, NH4+-, and NO3--N. Losses of NH 3 by volatilization with unamended UR ranged from 28 to 37% of the applied N, with peak of losses observed the third day after fertilization. NBPT delayed the peak of NH 3 losses due to urease inhibition and reduced NH 3 volatilization between 54 and 78% when compared with untreated UR. Up to 10 days after the fertilizer application, NH 3 losses had not been affected by DCD in the UR or the UR + NBPT treatments; thereafter, NH 3 volatilization tended to decrease, but not when DCD was present. As a consequence, the addition of DCD caused a 5-16% increase in NH 3 volatilization losses of the fertilizer N applied as UR from both the UR and the UR + NBPT treatments. Because the effectiveness of NBPT to inhibit soil urease activity was strong only in the first week, it could be concluded that DCD did not affect the action of NBPT but rather, enhanced volatilization losses by maintaining higher soil NH4+ concentration and pH for a longer time. Depending on the combination of factors influencing NH 3 volatilization, DCD could even offset the beneficial effect of NBPT in reducing NH 3 volatilization losses. © 2012 Elsevier Ltd.

Urea-induced unfolding of Glossoscolex paulistus hemoglobin, in oxy- and cyanomet-forms: A dissociation model

The urea effect on the giant extracellular hemoglobin of Glossoscolex paulistus (HbGp) stability was studied by analytical ultracentrifugation (AUC) and small angle X-ray scattering (SAXS). AUC data show that the sedimentation coefficient distributions curves c (S), at 1.0mol/L of urea, display a single peak at 57 S, associated to the undissociated protein. The increase in urea concentration, up to 4.0mol/L, induces the appearance of smaller species, due to oligomeric dissociation. The sedimentation coefficients and molecular masses are 9.2S and 204kDa for the dodecamer (abcd)3, 5.5S and 69kDa for the tetramer (abcd), 4.1S and 52kDa for the trimer (abc) and 2.0 S and 17kDa for the monomer d, respectively. SAXS data show initially a decrease in the I(0) values due to the oligomeric dissociation, and then, above 4.0mol/L of denaturant, for oxy-HbGp, and above 6.0mol/L for cyanomet-HbGp, an increase in the maximum dimension and gyration radius is observed, due to the unfolding process. According to AUC and SAXS data the HbGp unfolding is described by two phases: the first one, at low urea concentration, below 4.0mol/L, characterizes the oligomeric dissociation, while the second one, at higher urea concentration, is associated to the unfolding of dissociated species. Our results are complementary to a recent report based on spectroscopic observations. © 2012 Elsevier B.V.

AMMONIUM AND NITRATE IN SOIL AND RATOON SUGARCANE GROWN IN FUNCTION OF NITROGEN ON OXISOL

After harvest, sugarcane residues left on the soil surface can alter nitrogen (N) dynamics in the plant-soil system. In Oxisols, the nitrogen fertilizer applied had its effects on the levels of ammonium and nitrate in the soil, N concentration in the plant leaves, and on the growth and productivity of second ratoon plants. The N rates tested were of 0, 60, 120, 180, and 240 kg ha-1. Each treatment was replicated four times. Four months after the experiment was started, ammonium and nitrate concentration in the soil, N levels in plant leaves, and plant growth were evaluated. Productivity was evaluated 11 months after the experiment was set. By increasing the content of mineral N in soil, plant growth variables reflected differences in the production of stems; however, it did not affect foliar N. The use of leaf analysis was not important to assess the nutritional status of nitrogen in the ratoon sugarcane. Nitrogen concentration in soil was affected by nitrogen fertilization, but not the N content in leaves. The rate of 138 kg N ha-1enabled greater production of sugarcane stalks (140 t ha-1). © 2013 Copyright Taylor and Francis Group, LLC.

Development and application of an electronic tongue for detection and monitoring of nitrate, nitrite and ammonium levels in waters

This work presents the first study and development of an electronic tongue analysis system for the monitoring of nitrogen stable species: nitrate, nitrite and ammonium in water. The electronic tongue was composed of an array of 15 potentiometric poly(vinyl chloride) membrane sensors sensitive to cations and anions plus an artificial neural network (ANN) response model. The building of the ANN model was performed in a medium containing sodium, potassium, and chloride as interfering ions, thus simulating real environmental samples. The correlation coefficient in the cross-validation of nitrate, nitrite and ammonium was satisfactory in the three cases with values higher than 0.92. Finally, the utility of the proposed system is shown in the monitoring of the photoelectrocatalytic treatment of nitrate. © 2013 Elsevier B.V.

Fontes e doses de nitrogênio na nutrição, produção e qualidade do feijoeiro

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Manejo da adubação nitrogenada em híbridos de mamona de porte baixo cultivados na safra e na safrinha em sistema plantio direto

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

Fontes e doses de adubação nitrogenada na atividade microbiana, colonização micorrízica e fertilidade em solo com Brachiaria brizantha

Pós-graduação em Ciência Animal - FMVA