Thermally activated peroxydisulfate in the presence of additives: A clean method for the degradation of pollutants

The kinetics and mechanism of the thermal activation of peroxydisulfate, in the temperature range from 60 to 80 degrees C, was investigated in the presence and absence of sodium formate as an additive to turn the oxidizing capacity of the reaction mixture into a reductive one. Trichloroacetic acid, TCA, whose degradation by a reductive mechanism is well reported in the literature, was used as a probe. The chemistry of thermally activated peroxydisulfate is described by a reaction scheme involving free radical generation. The proposed mechanism is evaluated by a computer simulation of the concentration profiles obtained under different experimental conditions. In the presence of formate, SO(4)(center dot-) radicals yield CO(2)(center dot-), which are the main species available for degrading TCA. Under the latter conditions, TCA is more efficiently depleted than in the absence of formate, but otherwise identical conditions of temperature and [S(2)O(8)(2-)]. We therefore conclude that activated peroxydisulfate in the presence of formate as an additive is a convenient method for the mineralization of substrates that are refractory to oxidation. such as perchlorinated hydrocarbons and TCA. This method has the advantage that leaves no toxic residues. (C) 2009 Elsevier Ltd. All rights reserved.

Photoinduced Degradation of the Herbicide Clomazone Model Reactions for Natural and Technical Systems

The photodegradation of the herbicide clomazone in the presence of S(2)O(8)(2-) or of humic substances of different origin was investigated. A value of (9.4 +/- 0.4) x 10(8) m(-1) s(-1) was measured for the bimolecular rate constant for the reaction of sulfate radicals with clomazone in flash-photolysis experiments. Steady state photolysis of peroxydisulfate, leading to the formation of the sulfate radicals, in the presence of clomazone was shown to be an efficient photodegradation method of the herbicide. This is a relevant result regarding the in situ chemical oxidation procedures involving peroxydisulfate as the oxidant. The main reaction products are 2-chlorobenzylalcohol and 2-chlorobenzaldehyde. The degradation kinetics of clomazone was also studied under steady state conditions induced by photolysis of Aldrich humic acid or a vermicompost extract (VCE). The results indicate that singlet oxygen is the main species responsible for clomazone degradation. The quantum yield of O(2)(a(1)Delta(g)) generation (lambda = 400 nm) for the VCE in D(2)O, Phi(Delta) = (1.3 +/- 0.1) x 10(-3), was determined by measuring the O(2)(a(1)Delta(g)) phosphorescence at 1270 nm. The value of the overall quenching constant of O(2)(a(1)Delta(g)) by clomazone was found to be (5.7 +/- 0.3) x 10(7) m(-1) s(-1) in D(2)O. The bimolecular rate constant for the reaction of clomazone with singlet oxygen was k(r) = (5.4 +/- 0.1) x 10(7) m(-1) s(-1), which means that the quenching process is mainly reactive.

Galerkin Method and Weighting Functions Applied to Nonlinear H(infinity) Control with Output Feedback

This paper considers two aspects of the nonlinear H(infinity) control problem: the use of weighting functions for performance and robustness improvement, as in the linear case, and the development of a successive Galerkin approximation method for the solution of the Hamilton-Jacobi-Isaacs equation that arises in the output-feedback case. Design of nonlinear H(infinity) controllers obtained by the well-established Taylor approximation and by the proposed Galerkin approximation method applied to a magnetic levitation system are presented for comparison purposes.

Simple Excitation Model for Coaxial Driven Monopole Antennas

A new excitation model for the numerical solution of field integral equation (EFIE) applied to arbitrarily shaped monopole antennas fed by coaxial lines is presented. This model yields a stable solution for the input impedance of such antennas with very low numerical complexity and without the convergence and high parasitic capacitance problems associated with the usual delta gap excitation.

A method to estimate EMG crosstalk between two muscles based on the silent period following an H-reflex

The crosstalk phenomenon consists in recording the volume-conducted electromyographic activity of muscles other than that under study. This interference may impair the correct interpretation of the results in a variety of experiments. A new protocol is presented here for crosstalk assessment between two muscles based on changes in their electrical activity following a reflex discharge in one of the muscles in response to nerve stimulation. A reflex compound muscle action potential (H-reflex) was used to induce a silent period in the muscle that causes the crosstalk, called here the remote muscle. The rationale is that if the activity recorded in the target muscle is influenced by a distant source (the remote muscle) a silent period observed in the electromyogram (EMG) of the remote muscle would coincide with a decrease in the EMG activity of the target muscle. The new crosstalk index is evaluated based on the root mean square (RMS) values of the EMGs obtained in two distinct periods (background EMG and silent period) of both the remote and the target muscles. In the present work the application focused on the estimation of the degree of crosstalk from the soleus muscle to the tibialis anterior muscle during quiet stance. However, the technique may be extended to other pairs of muscles provided a silent period may be evoked in one of them. (C) 2009 IPEM. Published by Elsevier Ltd. All rights reserved.

Transport Barkhausen-like noise in uniaxially pressed Bi(1.65)Pb(0.35)Sr(2)Ca(2)Cu(3)O(10+delta) ceramic samples

We report on the detection of the transport Barkhausen-like noise (TBN) in polycrystalline samples of Bi(1.65)Pb(0.35)Sr(2)Ca(2) Cu(3)O(10+delta) (Bi-2223) which were subjected to different uniaxial compacting pressures. The transport Barkhausen-like noise was measured when the sample was subjected to an ac triangular-shape magnetic field (f similar to 1 Hz) with maximum amplitude B(max) approximate to 5.5 mT, in order to avoid the flux penetration within the superconducting grains. Analysis of the TBN signal, measured for several values of excitation current density, indicated that the applied magnetic field in which the noise signal first appears, B(a)(t(i)), is closely related to the magnetic-flux pinning capability of the material. The combined results are consistent with the existence of three different superconducting levels within the samples: (i) the superconducting grains; (ii) the superconducting clusters; and (iii) the weak-links. We finally argue that TBN measurements constitute a powerful tool for probing features of the intergranular transport properties in polycrystalline samples of high-T(c) superconductors. (C) 2010 Elsevier B.V. All rights reserved.

Experimental and theoretical study of transport properties in uniaxially pressed (Bi, Pb)(2)Sr(2)Ca(2)Cu(3)O(10+delta) ceramic samples

Experimental and theoretical studies on the magnetic field dependence of the electrical resistance R(B(a)) and the transport noise (TN) in polycrystalline high-T(c) superconductors subjected to different uniaxial compacting pressures were conducted. X-ray diffraction rocking curves were performed in different surfaces of the samples in order to investigated the degree of texture The results indicated an improvement of the degree of texture with increasing the uniaxial compacting pressure In theoretical simulations of the data, the polycrystalline superconductors were described as a series-parallel array of Josephson devices The intergranular magnetic field is described within the framework of the intragranular flux-trapping model and the distribution of the grain-boundary angles is assumed to follow the Rayleigh statistical function The proposed model describes well the experimental magnetoresistance R(B(a)) data We have found that the behavior of the R(B(a)) curves changes appreciably when different uniaxially compacting pressures are applied to the sample and such a changes are reproduced by the model when different grain-boundary angles distributions are used In addition, changes in the R(B(a)) dependence have their counterparts in the experimental transport noise signals (C) 2009 Elsevier B.V. All rights reserved

MULTIVARIATE STATISTICAL METHOD IN OPTIMIZATION OF PROTEIN EXTRACTION FROM SOYBEAN FLOUR WITH DAIRY WHEY

The aim objective of this project was to evaluate the protein extraction of soybean flour in dairy whey, by the multivariate statistical method with 2(3) experiments. Influence of three variables were considered: temperature, pH and percentage of sodium chloride against the process specific variable ( percentage of protein extraction). It was observed that, during the protein extraction against time and temperature, the treatments at 80 degrees C for 2h presented great values of total protein (5.99%). The increasing for the percentage of protein extraction was major according to the heating time. Therefore, the maximum point from the function that represents the protein extraction was analysed by factorial experiment 2(3). By the results, it was noted that all the variables were important to extraction. After the statistical analyses, was observed that the parameters as pH, temperature, and percentage of sodium chloride, did not sufficient for the extraction process, since did not possible to obtain the inflection point from mathematical function, however, by the other hand, the mathematical model was significant, as well as, predictive.

Extension of a Recent Method for Obtaining Exact Solutions of the Bruce and Klute Equation

A method based on a specific power-law relationship between the hydraulic head and the Boltzmann variable was recently presented. We generalized this relationship to a range of powers and extended the solution to include the saturated zone. As a result, the new solution satisfies the Bruce and Klute equation exactly.

Evaluation of FAO Penman-Monteith and alternative methods for estimating reference evapotranspiration with missing data in Southern Ontario, Canada

Grass reference evapotranspiration (ETo) is an important agrometeorological parameter for climatological and hydrological studies, as well as for irrigation planning and management. There are several methods to estimate ETo, but their performance in different environments is diverse, since all of them have some empirical background. The FAO Penman-Monteith (FAD PM) method has been considered as a universal standard to estimate ETo for more than a decade. This method considers many parameters related to the evapotranspiration process: net radiation (Rn), air temperature (7), vapor pressure deficit (Delta e), and wind speed (U); and has presented very good results when compared to data from lysimeters Populated with short grass or alfalfa. In some conditions, the use of the FAO PM method is restricted by the lack of input variables. In these cases, when data are missing, the option is to calculate ETo by the FAD PM method using estimated input variables, as recommended by FAD Irrigation and Drainage Paper 56. Based on that, the objective of this study was to evaluate the performance of the FAO PM method to estimate ETo when Rn, Delta e, and U data are missing, in Southern Ontario, Canada. Other alternative methods were also tested for the region: Priestley-Taylor, Hargreaves, and Thornthwaite. Data from 12 locations across Southern Ontario, Canada, were used to compare ETo estimated by the FAD PM method with a complete data set and with missing data. The alternative ETo equations were also tested and calibrated for each location. When relative humidity (RH) and U data were missing, the FAD PM method was still a very good option for estimating ETo for Southern Ontario, with RMSE smaller than 0.53 mm day(-1). For these cases, U data were replaced by the normal values for the region and Delta e was estimated from temperature data. The Priestley-Taylor method was also a good option for estimating ETo when U and Delta e data were missing, mainly when calibrated locally (RMSE = 0.40 mm day(-1)). When Rn was missing, the FAD PM method was not good enough for estimating ETo, with RMSE increasing to 0.79 mm day(-1). When only T data were available, adjusted Hargreaves and modified Thornthwaite methods were better options to estimate ETo than the FAO) PM method, since RMSEs from these methods, respectively 0.79 and 0.83 mm day(-1), were significantly smaller than that obtained by FAO PM (RMSE = 1.12 mm day(-1). (C) 2009 Elsevier B.V. All rights reserved.

Definition of priority areas for forest conservation through the ordered weighted averaging method

The general objective of this study was to evaluate the ordered weighted averaging (OWA) method, integrated to a geographic information systems (GIS), in the definition of priority areas for forest conservation in a Brazilian river basin, aiming at to increase the regional biodiversity. We demonstrated how one could obtain a range of alternatives by applying OWA, including the one obtained by the weighted linear combination method and, also the use of the analytic hierarchy process (AHP) to structure the decision problem and to assign the importance to each criterion. The criteria considered important to this study were: proximity to forest patches; proximity among forest patches with larger core area; proximity to surface water; distance from roads: distance from urban areas; and vulnerability to erosion. OWA requires two sets of criteria weights: the weights of relative criterion importance and the order weights. Thus, Participatory Technique was used to define the criteria set and the criterion importance (based in AHP). In order to obtain the second set of weights we considered the influence of each criterion, as well as the importance of each one, on this decision-making process. The sensitivity analysis indicated coherence among the criterion importance weights, the order weights, and the solution. According to this analysis, only the proximity to surface water criterion is not important to identify priority areas for forest conservation. Finally, we can highlight that the OWA method is flexible, easy to be implemented and, mainly, it facilitates a better understanding of the alternative land-use suitability patterns. (C) 2008 Elsevier B.V. All rights reserved.

Genetic Diversity and a PCR-Based Method for Xanthomonas axonopodis Detection in Passion Fruit

Xanthomonas axonopodis pv. passiflorae causes bacterial spot in passion fruit. It attacks the purple and yellow passion fruit as well as the sweet passion fruit. The diversity of 87 isolates of pv. passiflorae collected from across 22 fruit orchards in Brazil was evaluated using molecular profiles and statistical procedures, including an unweighted pair-group method with arithmetical averages-based dendrogram, analysis of molecular variance (AMOVA), and an assigning test that provides information on genetic structure at the population level. Isolates from another eight pathovars were included in the molecular analyses and all were shown to have a distinct repetitive sequence-based polymerase chain reaction profile. Amplified fragment length polymorphism technique revealed considerable diversity among isolates of pv. passiflorae, and AMOVA showed that most of the variance (49.4%) was due to differences between localities. Cluster analysis revealed that most genotypic clusters were homogeneous and that variance was associated primarily with geographic origin. The disease adversely affects fruit production and may kill infected plants. A method for rapid diagnosis of the pathogen, even before the disease symptoms become evident, has value for producers. Here, a set of primers (Xapas) was designed by exploiting a single-nucleotide polymorphism between the sequences of the intergenic 16S-23S rRNA spacer region of the pathovars. Xapas was shown to effectively detect all pv. passiflorae isolates and is recommended for disease diagnosis in passion fruit orchards.

Effectiveness of the standard evaluation method for hydraulic nozzles employed in stored grain protection trials

In stored grains, smaller depositions and great variation with respect to theoretical insecticide doses are frequently found. The objective of this work was to study the effectiveness of the standard method (ISO 5682/1-1996) employed to evaluate hydraulic nozzles used in stored corn and wheat grain protection experiments. The transversal volumetric distribution and droplet spectrum of a model TJ-60 8002EVS nozzle were determined in order to calibrate a spraying system for an application rate of 5 L/t and to obtain theoretical concentrations of 10 and 0.5 mg/kg of fenitrothion and esfenvalerate, respectively. After treatment, the corn and wheat grains were processed and deposition was analyzed by gas chromatography. The type of grain did not have any influence on insecticide deposition and was dependent upon insecticide only. The insecticide deposits on the grains only reached 42.1 and 38.2% of the intended theoretical values for fenitrothion and esfenvalerate concentrations, respectively. These results demonstrate the ineffectiveness of the standard evaluation method for hydraulic nozzles employed in stored grain protection experiments.

Method development and optimization for the determination of selenium in bean and soil samples using hydride generation electrothermal atomic absorption spectrometry

The present investigation is the first part of an initiative to prepare a regional map of the natural abundance of selenium in various areas of Brazil, based on the analysis of bean and soil samples. Continuous-flow hydride generation electrothermal atomic absorption spectrometry (HG-ET AAS) with in situ trapping on an iridium-coated graphite tube has been chosen because of the high sensitivity and relative simplicity. The microwave-assisted acid digestion for bean and soil samples was tested for complete recovery of inorganic and organic selenium compounds (selenomethionine). The reduction of Se(VI) to Se(IV) was optimized in order to guarantee that there is no back-oxidation, which is of importance when digested samples are not analyzed immediately after the reduction step. The limits of detection and quantification of the method were 30 ng L(-1) Se and 101 ng L(-1) Se, respectively, corresponding to about 3 ng g(-1) and 10 ng g(-1), respectively, in the solid samples, considering a typical dilution factor of 100 for the digestion process. The results obtained for two certified food reference materials (CRM), soybean and rice, and for a soil and sediment CRM confirmed the validity of the investigated method. The selenium content found in a number of selected bean samples varied between 5.5 +/- 0.4 ng g(-1) and 1726 +/- 55 ng g(-1), and that in soil samples varied between 113 +/- 6.5 ng g(-1) and 1692 +/- 21 ng g(-1). (C) 2011 Elsevier B.V. All rights reserved.

Validated method for the quantification of artepillin-C in Brazilian propolis

Brazilian propolis contains several phenolic compounds among which 5 diprenyl-4-hydroxycinnamic acid (artepillin-C) is commonly found in areas where flora is rich in Baccharis species. The quantification of artepillin-C has become an important factor as an indicator of Brazilian propolis quality and the compound may be used as a chemical marker for quality control in exportating green propolis. This work was to validate the method and evaluate the content of artepillin-C from 33 samples collected in different Brazilian regions. The method used was HPLC with UV-vis detection and a reversed-phase C-18 Column. The validation parameters studied were: linearity, accuracy, precision, quantification and detection limits. The results obtained were: detection limit = 0.0036 mu g/mL, quantification limit = 0.012 mu g/mL, accuracy = 0.0064 and 0.078, recovery 98-102%. Artepillin-C content varied from 0 to 11% depending on the geographical origin. Propolis from the southeast region presented the highest level of artepillin-C (5.0-11.0%). Whist that from the northeast region did not show any artepillin-C. Copyright (C) 2008 John Wiley & Sons, Ltd.