Investigação eletroquímica de alguns compostos organopaládio (ll): Determinação dos processos de redução do centro metálico em ciclopaladados

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

Reação de bis-inserção de 1,2-difenilacetileno na ligação Pd-C de ciclometalados

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

Brachiaria species affecting soil nitrification

O processo de nitrificação pode conduzir a perdas substanciais do nitrogênio aplicado por meio da lixiviação de nitrato e emissão de N2O. A regulação da nitrificação pode ser uma estratégia para melhorar a recuperação do N e aumentar sua eficiência agronômica. O objetivo deste trabalho foi avaliar a habilidade de espécies do gênero Brachiaria de inibir o processo de nitrificação no solo. O experimento foi realizado em casa de vegetação, em vasos contendo 10 dm³ de um Latossolo Vermelho. Os tratamentos foram constituídos do cultivo de três espécies forrageiras (Brachiaria brizantha, B. ruziziensis e B. decumbens) e quatro doses de N (0, 100, 200 e 300 mg/vaso), além da testemunha (sem a presença das forrageiras). Na ausência do cultivo de forrageiras, todos os níveis de adubação nitrogenada proporcionaram maior teor de N-NO3- no solo, reflexo da nitrificação. A mineralização da matéria orgânica supriu boa parte da necessidade de absorção de N pelas forrageiras estudadas, e a B. brizantha alterou a nitrificação em sua rizosfera, no entanto esse efeito não foi de magnitude suficiente para alterar o teor de N-NH4+ presente no volume total de solo do vaso.

Nitrate role in basic cation leaching under no-till

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

Crescimento de mudas de Gonçalo-Alves (Astronium fraxinifolium) sob diferentes fontes e doses de nitrogênio

A degradação do cerrado e a perda de sua biodiversidade demandam a revegetação de áreas desse bioma, onde existem espécies com potencial de uso econômico e ambiental pouco conhecidos. Este trabalho teve o objetivo de avaliar o efeito de diferentes fontes e doses de nitrogênio sobre o crescimento de mudas de Gonçalo-Alves (Astronium fraxinifolium), espécie arbórea nativa do cerrado ameaçada de extinção. O experimento foi realizado em estufa na UNESP/Campus de Ilha Solteira. O solo utilizado (Latossolo Vermelho) foi coletado na profundidade de 0,0 a 0,20 m, em Selvíria (MS). As fontes de nitrogênio utilizadas ((NH4)2SO4, NH4NO3 e Ca(NO3)2) foram aplicadas nas doses de 0; 50; 100; 150 e 200 mg dm-3. O N aplicado na forma de Ca(NO3)2 apresentou melhor resultado para o solo utilizado. O crescimento das mudas de Gonçalo-Alves não foi influenciado pelas diferentes fontes de N, mas respondeu às doses. A altura da planta, o diâmetro do coleto, o teor de clorofila foliar, o peso da matéria fresca e seca da parte aérea e do sistema radicular, o peso seco total, bem como o IQD e a razão entre o peso da matéria seca da parte aérea e do sistema radicular, apresentaram valor máximo para doses que variaram de 59,0 a 72,5 mg dm-3 de N, permitindo sugerir a dose de 72,5 mg dm-3 de N como suficiente para o crescimento satisfatório de mudas de Gonçalo-Alves.

Uniformidade de distribuição do potássio e do nitrogênio em sistema de irrigação por gotejamento

O uso da fertirrigação possibilita a obtenção de bons resultados, todavia é notada a necessidade de trabalhos que venham possibilitar a adoção correta da técnica. Dessa forma ,o presente trabalho buscou comparar a uniformidade de distribuição do potássio e do nitrogênio em sistema de irrigação por gotejamento. A solução de fertilizantes foi injetada durante 25 minutos, sendo recolhidas amostras de solução em diferentes momentos, durante e após ter sido finalizada a operação de injeção, tendo sido especificado o tempo de 35 minutos após o início da operação de injeção da solução de fertilizantes, como tempo-limite para a coleta da última amostra. As amostras coletadas tiveram os teores de potássio (K+) e nitrogênio (NO3- + NH4+) determinados. Com os resultados obtidos, concluiu-se que não houve variação significativa da uniformidade de distribuição de nitrogênio e de potássio no sistema de irrigação por gotejamento; maiores tempos de funcionamento de sistemas de irrigação, quando em operação de fertirrigação, possibilitam melhores uniformidades de distribuição do fertilizante, e deve-se calcular o tempo de lavagem do sistema de irrigação, pois é uma forma de melhorar a uniformidade de distribuição do fertilizante no campo.

Fungos anamorfos do solo da região dos lagos no Município de Santa Gertrudes, SP, Brasil

O solo do pólo cerâmico no município de Santa Gertrudes, SP, tem sido poluído há décadas por diversos elementos químicos, principalmente chumbo e zinco. Foram realizadas quatro coletas de amostras de solo, duas durante a época chuvosa e duas na seca, em cinco locais, de novembro de 2002 a junho de 2003, determinando-se temperatura, pH, teores de chumbo e zinco e a umidade do solo. Os fungos foram isolados pelo método de Warcup, modificado pelo preparo de suspensões aquosas de solo (1:10) e aplicação de 1 cm³ das suspensões sobre malte agar (2%), adicionado de Zn(NO3)2 e Pb(NO3)2 em concentrações crescentes: 0, 100, 200, 500 e 1.000 mg dm-3. Após cinco dias de incubação a 25 ºC, as colônias foram purificadas e identificadas. Foram obtidos 70 táxons de fungos anamorfos, com 70% de similaridade entre as micotas obtidas nos meios com os dois metais. Foram isolados 43 táxons nos meios de cultura com Pb(NO3)2, com predominância deles nas concentrações mais elevadas (500 a 1.000 mg dm-3). Foram obtidos 63 táxons nos meios com Zn(NO3)2, principalmente nas concentrações moderada e elevada (200 e 500 mg dm-3). Prevaleceram espécies de Trichoderma, de Penicillium e diversos fungos que são encontrados associados a substratos vegetais em decomposição. A tendência de se obter número elevado de táxons em meios de cultura com concentrações moderadas a elevadas de Zn e Pb pode ser justificada pela existência de bem adaptada e competitiva micota do solo, caracterizada por elevada capacidade de tolerância aos metais e eficiente habilidade sapróbia competitiva.

Nitrate reductase activity in leaves and stems of tanner grass (Brachiaria radicans Napper)

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

Evaluation and application of bismuth as an internal standard for the determination of lead in wines by simultaneous electrothermal atomic absorption spectrometry

A method for the direct determination of Pb in wines by simultaneous multi-element atomic absorption spectrometry (SIMAAS) using a transversely heated graphite atomizer, Zeeman-effect background corrector and internal standardization is proposed. Bismuth was used as an internal standard and Pd(NO3)(2) plus Mg(NO3)(2) as chemical modifier,to stabilize both the analyte and the internal standard. The implementation of two pyrolysis steps avoided any build-up of carbonaceous residues on the graphite platform. All diluted samples (1 + 1 v/v) in 0.2% v/v HNO3 and reference solutions (5.0-50 mug l(-1) Ph in 0.2% v/v HNO3) were spiked with 25 mug l(-1) Bi. For a 20 mul aliquot dispensed into the graphite tube, a good correlation (r = 0.9997) was obtained between the ratio of the analyte signal to the internal standard signal and the analyte concentration of the reference solutions. The electrothermal behaviour of Pb and Bi in red, white and rose wines were compared. In addition, absorbance variations due to changes in experimental conditions, such as atomizer temperature, integration time, injected sample volume, radiation beam intensity, graphite tube surface, dilution and sample composition, were minimized by using Bi as internal standard. Relative standard deviations of measurements based on integrated absorbance varied from 0.1 to 3.4% and from 0.5 to 7.3% (n = 12) with and without internal standard correction, respectively. Good recoveries (91-104%) for Pb spikes were obtained. The characteristic mass was 45 pg Pb and the limit of detection based on integrated absorbance was 0.9 mug l(-1) Pb. Internal standardization increased the lifetime of the tube by 25%. Direct determinations of Pb in wines with and without internal standardization approaches were in agreement at the 95% confidence level. The repeatability and the tube lifetime were improved when using Bi as internal standard. The improvement in accuracy using an internal standard was only observed when the analytical results were affected by errors.

Synthesis and characterization of PLZT (9/65/35) by the Pechini method and partial oxalate

ZrTiO4 (ZT), obtained by the Pechini method, was used as precursor for obtaining PLZT (lead lanthanum zirconium titanate). An aqueous solution of oxalic acid was prepared with particles of ZT, Pb(NO3)(2) and La2O3. After the PbC2O4 and La2O3 precipitate on ZT particles, the materials were calcined and X-ray diffraction (XRD) showed the cubic phase of PLZT. This material was sintered, in two steps, and a density of about 8.0 g/cm(3) was obtained. After the second sintering the XRD pattern showed the occurrence of tetragonal and rhombohedral phases. This was caused by a stoichiometric deviation and the material showed a high optical transparency. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Influence of the precursor salts in the synthesis of CaSnO3 by the polymeric precursor method

CaSnO3 was synthesized by the polymeric precursor method, using different precursor salts as (CH3COO)(2)Ca. H2O, Ca(NO3)(2). 4H(2)O, CaCl2. 2H(2)O and CaCO3, leading to different results. Powder precursor was characterized using thermal analysis. Depending on the precursor different thermal behaviors were obtained. Results also indicate the formation of carbonates, confirmed by IR spectra. After calcination and characterization by XRD, the formation of perovskite as single phase was only identified when calcium acetate was used as precursor. For other precursors, tin oxide was observed as secondary phase.

Effect of modifiers on thermal behaviour of Se in acid digestates and slurries of vegetables by graphite furnace atomic absorption spectrometry

The influence of sample preparation strategy of vegetables on the electrothermal behaviour of Se without and with chemical modifiers such as Pd(NO3)(2), Pd(NO3)(2) + Mg(NO3)(2), Pd(NO3)(2) + Cd(NO3)(2), pre-reduced Pd, Mg(NO3)(2), and Ni(NO3)(2) was investigated. Acid digestates and slurries of vegetables (0.1% m/v in 1% m/v HNO3 + 0.005% v/v of Triton X-100) were used to prepare reference solutions or slurries. For 10 mul of each modifier tested, pyrolysis and atomization temperatures were evaluated using pyrolysis and atomization curves, respectively. Best conditions, such as thermal stability, signal profile, repeatability and sensitivity were attained using Pd(NO3)(2) as chemical modifier. The following heating program (temperature, ramp/hold time) of the graphite tube of the Varian SpectrAA-800Z atomic absorption spectrometer was used: dry step (85 degreesC, 5/0 s; 95 degreesC, 40/0 s; 120 degreesC, 10/.5 s); pyrolysis step (1400 degreesC, 10/3s); atomization step (2200 degreesC, 1/2 s); clean step (2600 degreesC, 2/0 s). This pyrolysis temperature is 800 degreesC higher than when measuring without any modifier. For 20 muL sample volume and 10 mug Pd(NO3)(2), analytical curves in the 3.0-30 mug Se 1(-1) range were obtained. The method was applied for Se determination in acid digestates and slurries of 10 vegetable samples and one standard reference material (rice flower) and results were in agreement at 95% confidence level. Recoveries varied from 89 to 95% for spiked samples. The lifetime of the graphite tube was ca. 250 firings and the relative standard deviations (n = 12) for a typical acid digestate and slurry containing 20 mug Se 1(-1) were 3.8% and 8.3%, respectively. The limits of detection were 2.0 mug Se 1(-1) and 0.6 mug Se 1(-1) Se for digestates and slurries, respectively. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

Simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by GRAS with transversely heated graphite atomizer and longitudinal Zeeman-effect background correction

A method has been developed for the direct and simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by electrothermal atomic absorption spectrometry (ETAAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect back- ground correction. The thermal behavior of analytes during the pyrolysis and atomization stages was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3 and 1 + 1 (v/v) diluted water using mixtures of Pd(NO3)(2) + Mg(NO3)(2) as the chemical modifier, With 5 mug Pd + 3 mug Mg as the modifier, the pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1400degreesC and 2100degreesC, respectively, and 20 muL of the water sample (sample + 0.28 mol L-1 HNO3, 1 + 1, v/v), dispensed into the graphite tube, analytical curves were established ranging from 5.00 - 50.0 mug L-1 for As, Sb, Se; 10.0 - 100 mug L-1 for Cu; and 20.0 - 200 mug L-1 for Mn. The characteristic masses were around 39 pg As, 17 pg Cu, 60 pg Mn, 43 pg Sb, and 45 pg Se, and the lifetime of the tube was around 500 firings. The limits of detection (LOD) based on integrated absorbance (0.7 mug L-1 As, 0.2 mug L-1 Cu, 0.6 mug L-1 Mn, 0.3 mug L-1 Sb, 0.9 mug L-1 Se) exceeded the requirements of the Brazilian Food Regulations (decree # 310-ANVS from the Health Department), which established the maximum permissible level for As, Cu, Mn, Sb, and Se at 50 mug L-1, 1000 mug L-1, 2000 mug L-1, 5 mug L-1, and 50 mug L-1, respectively. The relative standard deviations (n = 12) were typically < 5.3% for As, < 0.5% for Cu, < 2.1% for Mn, < 11.7% for Sb, and < 9.2% for Se. The recoveries of As, Cu, Mn, Sb, and Se added to the mineral water samples varied from 102-111%, 91-107%, 92-109%, 89-97%, and 101-109%, respectively. Accuracy for the determination of As, Cu, Mu Sb and Se was checked using standard reference materials NIST SRM 1640 - Trace Elements in Natural Water, NIST SRM 1643d - Trace Elements in Water, and 10 mineral water samples. A paired t-test showed that the results were in agreement with the certified values of the standard reference materials at the 95% confidence level.

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.

Simultaneous determination of cadmium and lead in wine by electrothermal atomic absorption spectrometry

A method has been developed for the direct simultaneous determination of Cd and Pb in white and red wine by electrothermal atomic absorption spectrometry (ET-AAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect background correction. The thermal behavior of both analytes during pyrolysis and atomization stages were investigated in 0.028 mol l(-1) HNO3 and in 1 + 1 v/v diluted wine using mixtures of Pd(NO3)(2) + Mg(NO3)(2) and NH4H2PO4 + Mg(NO3)(2) as chemical modifiers. With 5 mug Pd + 3 mug Mg as the modifiers and a two-step pyrolysis (10 s at 400 degreesC and 10 s at 600 degreesC), the formation of carbonaceous residues inside the atomizer was avoided. For 20 mul of sample (wine + 0.056 mol l(-1) HNO3, 1 + 1, v/v) dispensed into the graphite tube, analytical curves in the 0.10-1.0 mug l(-1) Cd and 5.0-50 mug l(-1) Pb ranges were established. The characteristic mass was approximately 0.6 pg for Cd and 33 pg for Pb, and the lifetime of the tube was approximately 400 firings. The limits of detection (LOD) based on integrated absorbance (0.03 mug l(-1) for Cd, 0.8 mug l(-1) for Pb) exceeded the requirements of Brazilian Food Regulations (decree #55871 from Health Department), which establish the maximum permissible level for Cd at 200 mug l(-1) and for Pb at 500 mug l(-1). The relative standard deviations (n = 12) were typically < 8% for Cd and < 6% for Pb. The recoveries of Cd and Pb added to wine samples varied from 88 to 107% and 93 to 103%, respectively. The accuracy of the direct determination of Cd and Ph was checked for 10 table wines by comparing the results with those obtained for digested wine using single-element ET-AAS, which were in agreement at the 95% confidence level. (C) 2001 Elsevier B.V. B.V. All rights reserved.