Avaliação dos parâmetros de solubilidade de Hildebrand/Hansen na seleção de solventes para a extração de pesticidas organoclorados do solo

This work evaluated the use of the Hildebrand/Hansen solubility parameters for selection of solvents for extraction of the organochlorine pesticides pp' DDT, pp' DDE, Aldrin and a-Endossulfan from soil using columns packed with Al2O3. The mixtures hexane:dichloromethane (7:3; v/v), hexane:acetonitrile (1:1; v/v), hexane:acetone (1:1; v/v) and pure hexane were chosen as extracting solutions. In the addition and recovery tests, different extraction solutions provided high recoveries percentages (>75%) with coefficients of variation below 15%. The recoveries are in agreement with the Hildebrand/Hansen parameters, demonstrating its applicability in the selection of extracting solution and in the replacement of toxic solvents, as dichloromethane

External polyacrylate-coating as alternative material for preparation of photopolymerized sol-gel monolithic column

Photopolymerized sol-gel monolithic columns for use in capillary electrochromatography were prepared in 125 mu m i.d. polyacrylate-coated fused-silica capillaries. The polyacrylate-coating, unlike the polyimide one, is transparent to the radiation used (approximate to 370 nm), and thus, no coating removal is necessary. This is a very important particularity since intrinsic capillary column characteristics, such as flexibility and mechanical resistance, are unchanged. A mixture containing metacryloxypropyltrimethoxysilane (MPTMS) as the polymeric precursor, hydrochloric acid as the catalyst, toluene as the porogen and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819) as the photoinitiator was irradiated at 370 nm for 20 min inside the capillaries to prepare the columns through sol-gel approach. The versatility and viability of the use of polyacrilate as a new capillary external coating were shown through preparation of two columns under different conditions, which were tested in electrochromatography for separation of standard mixture containing thiourea (marker compound), propylbenzene, phenanthrene and pyrene. (C) 2008 Elsevier B.V. All rights reserved.

Resposta do capim-tanzânia à aplicação de soro ácido de leite

O objetivo deste trabalho foi avaliar a produção de matéria seca e a quantidade de nutrientes extraída por Panicum maximum Jacq. cv. Tanzânia adubado com soro ácido de leite. Amostras de um Argissolo foram coletadas nas profundidades de 0-20, 20-40 e 40-60 cm e colocadas em colunas de PVC compostas por três anéis correspondentes a cada camada. As doses de soro foram definidas com base na concentração de K, de modo a adicionar ao solo 0, 75, 150, 225 e 300 kg/ha de K2O em cada uma das três aplicações: antes da semeadura, após o primeiro e após o segundo corte. O experimento foi realizado em casa de vegetação em delineamento inteiramente ao acaso, durante 112 dias. Após esse período, as colunas foram desmontadas e o solo foi amostrado para análise. A aplicação de soro aumentou a produção de matéria seca; a produção máxima teórica total dos três cortes foi obtida com a aplicação acumulada de 390 m³/ha. As quantidades de K, P e Ca absorvidas pela planta e o teor de K no solo aumentaram significativamente com as doses de soro.

Nitrato em alface e mobilidade do íon em solo adubado com composto de lixo urbano

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

Potencial de lixiviação de herbicidas utilizados na cultura do algodão em colunas de solo

O intenso uso de herbicidas implica a necessidade de determinar o potencial dessas substâncias em contaminar fontes aquáticas subsuperficiais. Diante dessa preocupação, o objetivo deste trabalho foi avaliar o efeito de diferentes lâminas de água sobre o potencial de lixiviação de quatro herbicidas utilizados em pré-emergência na cultura do algodão, em dois solos provenientes de Campo Novo do Parecis-MT (RQ - textura arenosa) e Tangará da Serra-MT (LV - textura argilosa). No desenvolvimento deste trabalho utilizouse a técnica de bioensaio em colunas de solo, nas quais foram simuladas irrigações de 0, 20, 40, 60, 80 e 100 mm, após a aplicação de alachlor (RQ 2,40; LV 3,36 kg ha-1), oxyfluorfen (RQ 0,48; LV 0,72 kg ha-1), prometryne (RQ 0,75; LV 1,50 kg ha-1) e S-metolachlor (RQ 1,20; LV 1,44 kg ha-1). Nas amostras de solo com textura arenosa (RQ), evidenciou-se que lâminas de 80 e 100 mm de água proporcionaram lixiviação até a profundidade de 10-15 cm do alachlor e até 15-20 cm do S-metolachlor. Independentemente da lâmina de água aplicada, nas amostras de RQ oxyfluorfen não ultrapassou a camada de 5-10 cm, e o prometryne movimentou-se até a camada de 10-15 cm somente na lâmina de 100 mm de água. Nas amostras de solo com textura argilosa (LV), o oxyfluorfen não se movimentou além da camada superficial, mesmo sob as maiores lâminas de irrigação, e o prometryne atingiu 5-10 cm de profundidade sob lâminas de 80 e 100 mm. Os herbicidas alachlor e S-metolachlor atingiram 10-15 cm de profundidade sob lâminas de 80 e 100 mm no LV. Evidenciou-se uma maior movimentação efetiva das moléculas de herbicidas nas amostras de solo com textura arenosa (RQ), em relação às amostras de solo com textura argilosa (LV).

Extraction and clean-up procedure for analysis of organochlorine pesticide residues in ethoxylated lanolin

In the present study an evaluation was made of a method for the determination of organochlorine pesticide residues in ethoxylated lanolin. Samples were homogenized with Celite, transferred to chromatographic columns, prepacked with silica gel deactivated to 10%. The pesticide elution was processed with n-hexane-dichloromethane and the concentrated eluate was analyzed using gas-liquid chromatography (GC) with electron capture detection (ECD). The composition of the elution solvent was a significant factor for the recovery of the pesticides. Mean recoveries obtained for fortified samples ranged from 87 to 94% for p,p'-DDE, dieldrin, endrin, p,p'-DDD and p,p'-DDT. Optimization of the experimental conditions resulted in a small-scale method that combines extraction and cleanup in a single step. (C) 2000 Elsevier B.V. S.A. All rights reserved.

Three-parameter soil-water transient equations in horizontal water-transport analysis

For data obtained from horizontal soil column experiments, the determination of soil-water transport characteristics and functions would be aided by a single-form equation capable of objectively describing water content theta vs. time t at given position x(f). Our study was conducted to evaluate two such possible equations, one having the form of the Weibull frequency distribution, and the other being called a bipower form. Each equation contained three parameters, and was fitted by nonlinear least squares to the experimental data from three separate columns of a single soil. Across the theta range containing the measured data points obtained by gamma-ray attenuation, the two equations were in close agreement. The resulting family of theta(x(f),t) transients, as obtained from either equation, enabled the evaluation of exponent n in the t(n) dependence of the positional advance of a given theta. Not only was n found to be <0.5 at low theta values, but it also increased with theta and tended toward 0.5 as theta approached its sated (near-saturated) value. Some quantitative uncertainty in n(theta) does arise due to the reduced number of data points available at the higher water contents. Without claiming non-Boltzmann behavior (n < 0.5) as necessarily representative of all soils, we nonetheless consider n(theta) to be worthy of further study for evaluating its significance and implications.

PURIFICATION AND PROPERTIES OF SHIKIMATE DEHYDROGENASE FROM CUCUMBER (CUCUMIS-SATIVUS L)

Shikimate dehydrogenase (SDH, EC 1.1.1.25) extracted from cucumber pulp (Cucumis sativus L.) was purified 7-fold by precipitation with ammonium sulfate and elution from columns of Sephadex G-25, DEAE-cellulose, and hydroxyapatite. Two activity bands were detected on polyacrylamide gel electrophoresis at the last purification step. pH optimum was 8.7, and molecular weight of 45 000 was estimated on a Sephadex G-100 column. SDH was inhibited competitively by protocatechuic acid with a K(i) value of 2 x 10-4 M. K(m) values of 6 x 10-5 and 1 x 10-5 M were determined for shikimic acid and NADP+, respectively. The enzyme was completely inhibited by HgCl2 and p-(chloromercuri)benzoate (PCMB). NaCl and KCl showed partial protection against inhibition by PCMB. Heat inactivation between 50 and 55-degrees-C was biphasic, and the enzyme was completely inactivated after 10 min at 60-degrees-C. Incubation of SDH with either NADP+ or shikimic acid protected the enzyme against heat inactivation.

On non-ideal simple portal frame structural model: Experimental results under a non-ideal excitation

We present measurements of the non-linear oscillations of a portal frame foundation for a non-ideal motor. We consider a three-time redundant structure with two columns, clamped in their bases and a horizontal beam. An electrical unbalanced motor is mounted at mid span of the beam. Two non-linear phenomena are studied: a) mode saturation and energy transfer between modes; b) interaction between high amplitude motions of the structure and the rotation regime of a real limited power motor. The dynamic characteristics of the structure were chosen to have one-to-two internal resonance between the anti-symmetrical mode (sway motions) and the first symmetrical mode natural frequencies. As the excitation frequency reaches near resonance conditions with the 2nd natural frequency, the amplitude of this mode grows up to a certain level and then it saturates. The surplus energy pumped into the system is transferred to the sway mode, which experiences a sudden increase in its amplitude. Energy is transformed from low amplitude high frequency motion into high amplitude low frequency motion. Such a transformation is potentially dangerous.We consider the fact that real motors, such as the one used in this study, have limited power output. In this case, this energy source is said to be non-ideal, in contrast to the ideal source whose amplitude and frequency are independent of the motion of the structure. Our experimental research detected the Sommerfeld Effect: as the motor accelerates to reach near resonant conditions, a considerable part of its output energy is consumed to generate large amplitude motions of the structure and not to increase its own angular speed. For certain parameters of the system, the motor can get stuck at resonance not having enough power to reach higher rotation regimes. If some more power is available, jump phenomena may occur from near resonance to considerably higher motor speed regimes, no stable motions being possible between these two.

Evaluation of a double-setting alpha-tricalcium phosphate cement in eviscerated rabbit eyes

Purpose: To evaluate the macroscopy, microstructure, and tissue reaction of a double-setting a-tricalcium phosphate bone cement used as an intraocular implant in rabbits.Methods: the internal and external surface of the double-setting a-tricalcium phosphate implant was analyzed macroscopically and by scanning electron microscopy. Twelve New Zealand rabbits received 12-mm implants made of double-setting alpha-tricalcium phosphate cement after unilateral evisceration. Clinical evaluation was performed daily for the first 15 days after surgery and at 15-day intervals until the end of the study period. For histopathologic analysis, 3 animals per experimental period were submitted to enucleation at 15, 45, 90, and 180 days.Results: on gross inspection, the external surface of the implant was solid, smooth, and compact. The microarchitecture was characterized by the formation of columns of hexagonal crystals with interconnecting channels forming micropores. No wound dehiscence, signs of infection, or implant extrusion were observed in any animal throughout the study period. Histologic examination revealed the formation of fibrovascular tissue surrounding the implants, and there were signs of minimal integration of the surface limiting the fibrocellular cap with the space previously occupied by the implant.Conclusions: the double-setting alpha-tricalcium phosphate implant behaved as an inert and nonintegratable material. The lack of incorporation of this material by fibrovascular tissue is related to its characteristics of compactness and high resistance.

Influence of temperature on the properties of the xylanolytic enzymes of the thermotolerant fungus Aspergillus phoenicis

This study reports on the effects of growth temperature on the secretion and some properties of the xylanase and beta-xylosidase activities produced by a thermotolerant Aspergillus phoenicis. Marked differences were observed when the organism was grown on xylan-supplemented medium at 25 degreesC or 42 degreesC. Production of xylanolytic enzymes reached maximum levels after 72 h of growth at 42 degreesC; and levels were three- to five-fold higher than at 25 degreesC. Secretion of xylanase and beta-xylosidase was also strongly stimulated at the higher temperature. The optimal temperature was 85 degreesC for extracellular and 90 degreesC for intracellular beta-xylosidase activity, independent of the growth temperature. The optimum temperature for extracellular xylanase increased from 50 degreesC to 55 degreesC when the fungus was cultivated at 42 degreesC. At the higher temperature, the xylanolytic enzymes produced by A. phoenicis showed increased thermo stability, with changes in the profiles of pH optima. The chromatographic profiles were distinct when samples obtained from cultures grown at different temperatures were eluted from DEAE-cellulose and Biogel P-60 columns.

NATURAL ELONGATION OF SPHERICAL TOKAMAKS

The variation of the elongation of axisymmetric plasma columns in vertical equilibrium magnetic fields is investigated as a function of the aspect ratio using the Solov'ev equilibrium model and the principle of virtual casing.

Cytoarchitecture and musculotopic organization of the facial motor nucleus in Cebus apella monkey

The architecture and musculotopic organization of the facial motor nucleus in the Cebus apella monkey (a New World primate) were investigated using histological techniques and a multiple labelling strategy, in which horseradish peroxidase-conjugated neuroanatomical tracers (CTB-HRP and WGA-HRP) and fluorescent tracers were injected into individual facial muscles. The facial motor nucleus was formed by multipolar motoneurons and had an ovoid shape, with its rostrocaudal axis measuring on average 1875 mum. We divided the nucleus into four different subnuclei: medial, intermediate, dorsal and lateral. Retrograde labelling patterns revealed that individual muscles were innervated by longitudinal functional columns of motoneurons. The columns of the orbicularis oculi, zygomaticus, orbicularis oris, auricularis superior, buccinator and platysma muscles were located in the dorsal, intermediate, lateral, medial, lateral and intermediate subnuclei, respectively. However, the motoneuron columns of the levator labii superioris alaeque nasi muscle and frontalis muscle could not be associated with a specific subnucleus. The present results confirm previous studies regarding the musculotopic organization of the facial motor nucleus. However, we observed some particularities in terms of the relative size of each column in C. apella, which might be related to the functional and behavioral importance of each muscle in the particular context of this primate.

Partial purification and some properties of a T2 ribonuclease from Aspergillus flavipes

A ribonuclease was partially purified from the culture medium of Aspergillus flavipes (IZ:1501), after 96 h of cultivation by chromatography on DEAE-cellulose and Sephadex G100 columns. The molecular weight of the RNase was estimated to be 40 kD by gel filtration using Sephadex G100, and the optimum pH and temperature were 4.0 and 50-55 degrees C, respectively. Catalytic activity was inhibited by Zn+2, Fe+3, Hg+2 and Ag+ ions. The enzyme did not show an exact base specificity and produced four kinds of 3'-nucleotides from yeast RNA.

Effect of a pilot washing system on dicofol levels in orange matrix

An efficient analytical method is described for the analysis of dicofol residues in pulp and orange peel. Samples are mixed with Celite and transferred to chromatographic columns prepacked with silica gel. Dicofol is eluted with ethyl acetate, and the extracts are analyzed by gas chromatography with electron capture detection. Mean recoveries for dicofol at levels of 0.5, 2.0, 5.0, and 10 mg/kg ranged from 87 to 95% with relative standard deviation values between 2.6 and 9.0%. To investigate the effect of a pilot washing system on dicofol residues in oranges, the analytical procedure was applied to samples submitted to different treatments with commercial formulations under field and laboratory conditions. The orange samples with and without washing were analyzed in duplicate, and the results indicated that washing under the described conditions did not allow a complete removal of dicofol residues from orange peel.