Estimation of travel time on urban networks with midlink sources and sinks

This paper presents a methodology for estimation of average travel time on signalized urban networks by integrating cumulative plots and probe data. This integration aims to reduce the relative deviations in the cumulative plots due to midlink sources and sinks. During undersaturated traffic conditions, the concept of a virtual probe is introduced, and therefore, accurate travel time can be obtained when a real probe is unavailable. For oversaturated traffic conditions, only one probe per travel time estimation interval—360 s or 3% of vehicles traversing the link as a probe—has the potential to provide accurate travel time.

Visualization of water vapour flow in a packed bed adsorber by near-infrared diffused transmittance tomography

This work presents a procedure based on spatially-resolved near-infrared imaging, in order to observe temperature and composition maps in gas-solid packed beds subjected to effects of aspect ratio and non-isothermal conditions. The technique was applied to the water vapour flow in a packed bed adsorber of low aspect ratio, filled with silica gel, using a tuneable diode laser, focal planar array detector and tomographic reconstruction. The 2D projected images from parallel scanning permitted data to be retrieved from the packing and above the packing sections of 12.0×12.0×18.2mm at a volume-resolution of 0.15×0.15×0.026mm and a time-resolution of less than 3min. The technique revealed uneven temperature and composition maps in the core packed bed and in the vicinity of the wall due to flow maldistribution. In addition, the heat uptake from the packed bed and local cross-mixing were experimentally ascertained by local profiles of the water vapour composition and temperature under various aspect ratios and feed flow rates. The relative deviations in temperature and compositions were 11.1% and 9.3%, respectively. The deviation in composition, which covers the packing and above the packing sections, was slightly higher than the deviation of 8% obtained up-to-date but was limited to the exit of a packed bed adsorber. © 2011.

Determination of free furfuryl alcohol in foundry resins by chromatographic techniques

Two chromatographic methods, gas chromatography with flow ionization detection (GC–FID) and liquid chromatography with ultraviolet detection (LC–UV), were used to determine furfuryl alcohol in several kinds of foundry resins, after application of an optimised extraction procedure. The GC method developed gave feasibility that did not depend on resin kind. Analysis by LC was suitable just for furanic resins. The presence of interference in the phenolic resins did not allow an appropriate quantification by LC. Both methods gave accurate and precise results. Recoveries were >94%; relative standard deviations were ≤7 and ≤0.3%, respectively for GC and LC methods. Good relative deviations between the two methods were found (≤3%).

Electroanalytical determination of codeine in pharmaceutical preparations

A square wave voltammetric (SWV) method and a flow injection analysis systemwi th electrochemical detection (FIA-EC) using a glassy carbon electrode were evaluated for the determination of codeine in pharmaceutical preparations. The interference of several compounds, such as acetaminophen,guaiacol, parabens, ephedrine, acetylsalicylic acid and caffeine, that usually appear associated with codeine pharmaceutical preparations was studied. It was verified that these electroanalytical methods could not be used with acetaminophen present in the formulations and that with guaiacol, parabens or ephedrine present the use of the FIA-EC system was impracticable. A detection limit of 5 µmol L- 1 and a linear calibration range from 40 to 140 µmol L- 1 was obtained with the SWV method. For the flow injection analysis procedure a linear calibration range was obtained from 7 to 50 µmol L- 1 with a detection limit of 3 µmol L- 1 and the FIA-EC systemallowed a sampling rate of 115 samples per hour. The results obtained by the two methods, SWV and FIA-EC, were compared with those obtained using reference methods and demonstrated good agreement, with relative deviations lower than 4%.

Electroanalytical study of the pesticide asulam

The electrochemical behaviour of the herbicide Asulam was studied by cyclic and square wave voltammetry. Asulam may be irreversibly oxidised at a glassy carbon electrode. Maximum currents were obtained at pH=1.9 in aqueous electrolyte solution. Based on the electrochemical behaviour of Asulam, two analytical methodologies were developed for its determination in water samples, using square wave voltammetry (SWV) and flow injection analysis (FIA) coupled with an amperometric detector. Limits of detection of 7.1x10-6 mol L-1 and 1.2x10-8 mol L-1 for SWV and FIA respectively, were achieved. Repeatability was calculated by assessing the relative standard deviation (%) for 10 consecutive determinations of one sample. The found values were 2.1% for SWV and 5.0% for FIA. Validation of the results provided by SWV and FIA methodologies was performed by comparison with results from an HPLC-DAD technique. Good relative deviations were found (<5%). Recovery trials were performed to assess the accuracy of the results and the obtained values were between 84% and 107% for both methods.

Chromatographic techniques for the determination of free phenol in foundry resins

Phenol is a toxic compound present in a wide variety of foundry resins. Its quantification is important for the characterization of the resins as well as for the evaluation of free contaminants present in foundry wastes. Two chromatographic methods, liquid chromatography with ultraviolet detection (LC-UV) and gas chromatography with flame ionization detection (GC-FID), for the analysis of free phenol in several foundry resins, after a simple extraction procedure (30 min), were developed. Both chromatographic methods were suitable for the determination of phenol in the studied furanic and phenolic resins, showing good selectivity, accuracy (recovery 99–100%; relative deviations <5%), and precision (coefficients of variation <6%). The used ASTM reference method was only found to be useful in the analysis of phenolic resins, while the LC and GC methods were applicable for all the studied resins. The developed methods reduce the time of analysis from 3.5 hours to about 30 min and can readily be used in routine quality control laboratories.

Electroanalytical study of the pesticide ethiofencarb

A detailed study of voltammetric behavior of ethiofencarb (ETF) is reported using glassy carbon electrode (GCE) and hanging mercury drop electrode (HMDE). With GCE, it is possible to verify that the oxidative mechanism is irreversible, independent of pH, and the maximum intensity current was observed at +1.20 V vs. AgCl/Ag at pH 1.9. A linear calibration line was obtained from 1.0x10-4 to 8.0x10-4 mol L-1 with SWV method. To complete the electrochemical knowledge of ETF pesticide, the reduction was also explored with HMDE. A well-defined peak was observed at –1.00V vs. AgCl/Ag in a large range of pH with higher signal at pH 7.0. Linearity was obtained in 4.2x10-6 and 9.4x10-6 mol L-1 ETF concentration range. An immediate alkaline hydrolysis of ETF was executed, producing a phenolic compound (2-ethylthiomethylphenol) (EMP), and the electrochemical activity of the product was examined. It was deduced that it is oxidized on GCE at +0.75V vs. AgCl/Ag with a maximum peak intensity current at pH 3.2, but the compound had no reduction activity on HMDE. Using the decrease of potential peak, a flow injection analysis (FIA) system was developed connected to an amperometric detector, enabling the determination of EMP over concentration range of 1.0x10-7 and 1.0x10-5 mol L-1 at a sampling rate of 60 h-1. The results provided by FIA methodology were performed by comparison with results from high-performance liquid chromatography (HPLC) technique and demonstrated good agreement with relative deviations lower than 4%. Recovery trials were performed and the obtained values were between 98 and 104%.

Comparação entre planejamento estatístico experimental e análise dimensional em operações de mistura e separação para sistema óleo-água

This work aims to determine a better methodology to help predicting some operational parameters to a new design of mixer-settler on treating wastewater produced by petroleum industry, called MDIF (Misturador-Decantador à Inversão de Fases/ Mixer-Settler based on Phase Inversion MSPI). The data from this research were obtained from the wastewater treatment unit, called MSPI-TU, installed on a wastewater treatment plant (WTP) of PETROBRAS/UO-RNCE. The importance in determining the better methodology to predict the results of separation and extraction efficiency of the equipment, contributes significantly to determine the optimum operating variables for the control of the unit. The study was based on a comparison among the experimental efficiency (E) obtained by operating MSPI-TU, the efficiency obtained by experimental design equation (Eplan) from the software Statistica Experimental Design® (version 7.0), and the other obtained from a modeling equation based on a dimensional analysis (Ecalc). The results shows that the experimental design equation gives a good prediction of the unit efficiencies with better data reliability, regarding to the condition before a run operation. The average deviation between the proposed by statistic planning model equation and experimental data was 0.13%. On the other hand, the efficiency calculated by the equation which represents the dimensional analysis, may result on important relative deviations (up 70%). Thus, the experimental design is confirmed as a reliable tool, with regard the experimental data processing of the MSPI-TU

Kinetics of osmotic dehydration and air-drying of pumpkins (Cucurbita moschata)

Kinetics of osmotic dehydration (OD) and effects of sucrose impregnation on thermal air-drying of pumpkin slices were investigated. A simplified model based on the solution of Fick's Law was used to estimate effective diffusion coefficients during OD and air-drying. In order to take into account shrinkage, average and variable thicknesses were considered. Pumpkin slices were dehydrated in sucrose solutions (40%, 50% and 60%, w/w, 27 degrees C. The effective water diffusion coefficients were higher than the sucrose, and low diffusivity dependence with solution concentration was observed. Samples non-treated and pre-treated in 60% osmotic solutions during one hour were dried in a hot-air-dryer at 50 and 70 degrees C (2 m/s) until equilibrium was achieved. Pre-treatment enhanced mass transfer during air-drying. Great volume reduction was observed in pre and non-treated dried samples. Using variable thickness in the model diminished the relative deviations between predicted and experimental OD and drying data. (C) 2007 Elsevier Ltd. All rights reserved.

A Simple maxwell Based Model in Order to Represent the frequency-dependent viscosity measured by ultrasound

A previous work showed that viscosity values measured high frequency by ultrasound agreed with the values at low frequency by the rotational viscometer when conditions are met, such as relatively low frequency viscosity. However, these conditions strongly reduce the range of the measurement cell. In order to obtain a measurement range and sensitivity high frequency must used, but it causes a frequency-dependent decrease on the viscosity values. This work introduces a new simple in order to represent this frequency-dependent behavior.model is based on the Maxwell model for viscoelastic , but using a variable parameter. This parameter has physical meaning because it represents the linear behavior the apparent elasticity measured along with the viscosity by .Automotive oils SAE 90 and SAE 250 at 22.5±0.5oC viscosities at low frequency of 0.6 and 6.7 Pa.s, respectively,tested in the range of 1-5 MHz. The model was used in to fit the obtained data using an algorithm of non-linear in Matlab. By including the viscosity at low frequency an unknown fitting parameter, it is possible to extrapolate its . Relative deviations between the values measured by the and extrapolated using the model for the SAE 90 and SAE 250 oils were 5.0% and 15.7%, respectively.©2008 IEEE.

Determination of salicylate in blood serum using an amperometric biosensor based on salicylate hydroxylase immobilized in a polypyrrole-glutaraldehyde matrix

The use of an amperometric biosensor for the salicylate determination in blood serum is described. The biosensor is based on salicylate hydroxylase (EC 1.14.13.1) electropolymerized onto a glassy carbon-working electrode with polypyrrole and glutaraldehyde, to improve the biosensor lifetime. The hexacyanoferrate (II) was also incorporated to work as a redox mediator to minimize possible interferences. The salicylate is enzymatically converted to catechol, which is monitored amperometrically by its electrooxidation at +0.170 V versus SCE (saturated calomel electrode). Salicylate determination was carried out maintaining the ratio between β-NADH and salicylate at 4:1 (30°C). The amperometric response of the biosensor was linearly proportional to the salicylate concentration between 2.3 x 10-6 and 1.4 x 10-5 mol l- 1, in 0.1 mol l-1 phosphate buffer (pH 7.8), containing 0.1 mol l-1 KCl and 5.0 x 10-4 mol l-1 Na2H2EDTA, as supporting electrolyte. The recovery studies, in the presence of several interfering compounds, showed recoveries between 96.4 and 104.8%. The useful lifetime of the biosensor in the concentration range evaluated was at least 40 days, in continuous use. Blood serum samples analyzed by this biosensor showed a good correlation compared to the spectrophotometric method (Trinder) used as reference, presenting relative deviations lower than 7.0%. (C) 2000 Elsevier Science B.V.

Direct Determination of Sugar Cane Quality Parameters by X-ray Spectrometry and Multivariate Analysis

Current methods for quality control of sugar cane are performed in extracted juice using several methodologies, often requiring appreciable time and chemicals (eventually toxic), making the methods not green and expensive. The present study proposes the use of X-ray spectrometry together with chemometric methods as an innovative and alternative technique for determining sugar cane quality parameters, specifically sucrose concentration, POL, and fiber content. Measurements in stem, leaf, and juice were performed, and those applied directly in stem provided the best results. Prediction models for sugar cane stem determinations with a single 60 s irradiation using portable X-ray fluorescence equipment allows estimating the % sucrose, % fiber, and POL simultaneously. Average relative deviations in the prediction step of around 8% are acceptable if considering that field measurements were done. These results may indicate the best period to cut a particular crop as well as for evaluating the quality of sugar cane for the sugar and alcohol industries.

Measurement and modeling of cloud condensation nuclei in continental air

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. Knowledge of the spatial and temporal distribution of CCN in the atmosphere is essential to understand and describe the effects of aerosols in meteorological models. In this study, CCN properties were measured in polluted and pristine air of different continental regions, and the results were parameterized for efficient prediction of CCN concentrations.The continuous-flow CCN counter used for size-resolved measurements of CCN efficiency spectra (activation curves) was calibrated with ammonium sulfate and sodium chloride aerosols for a wide range of water vapor supersaturations (S=0.068% to 1.27%). A comprehensive uncertainty analysis showed that the instrument calibration depends strongly on the applied particle generation techniques, Köhler model calculations, and water activity parameterizations (relative deviations in S up to 25%). Laboratory experiments and a comparison with other CCN instruments confirmed the high accuracy and precision of the calibration and measurement procedures developed and applied in this study.The mean CCN number concentrations (NCCN,S) observed in polluted mega-city air and biomass burning smoke (Beijing and Pearl River Delta, China) ranged from 1000 cm−3 at S=0.068% to 16 000 cm−3 at S=1.27%, which is about two orders of magnitude higher than in pristine air at remote continental sites (Swiss Alps, Amazonian rainforest). Effective average hygroscopicity parameters, κ, describing the influence of chemical composition on the CCN activity of aerosol particles were derived from the measurement data. They varied in the range of 0.3±0.2, were size-dependent, and could be parameterized as a function of organic and inorganic aerosol mass fraction. At low S (≤0.27%), substantial portions of externally mixed CCN-inactive particles with much lower hygroscopicity were observed in polluted air (fresh soot particles with κ≈0.01). Thus, the aerosol particle mixing state needs to be known for highly accurate predictions of NCCN,S. Nevertheless, the observed CCN number concentrations could be efficiently approximated using measured aerosol particle number size distributions and a simple κ-Köhler model with a single proxy for the effective average particle hygroscopicity. The relative deviations between observations and model predictions were on average less than 20% when a constant average value of κ=0.3 was used in conjunction with variable size distribution data. With a constant average size distribution, however, the deviations increased up to 100% and more. The measurement and model results demonstrate that the aerosol particle number and size are the major predictors for the variability of the CCN concentration in continental boundary layer air, followed by particle composition and hygroscopicity as relatively minor modulators. Depending on the required and applicable level of detail, the measurement results and parameterizations presented in this study can be directly implemented in detailed process models as well as in large-scale atmospheric and climate models for efficient description of the CCN activity of atmospheric aerosols.

Saddlepoint Approximations to the Probability of Ruin in Finite Time for the Compound Poisson Risk Process Perturbed by Diffusion

A large deviations type approximation to the probability of ruin within a finite time for the compound Poisson risk process perturbed by diffusion is derived. This approximation is based on the saddlepoint method and generalizes the approximation for the non-perturbed risk process by Barndorff-Nielsen and Schmidli (Scand Actuar J 1995(2):169–186, 1995). An importance sampling approximation to this probability of ruin is also provided. Numerical illustrations assess the accuracy of the saddlepoint approximation using importance sampling as a benchmark. The relative deviations between saddlepoint approximation and importance sampling are very small, even for extremely small probabilities of ruin. The saddlepoint approximation is however substantially faster to compute.

Determinação a baixo custo de açúcares redutores totais em caldo-de-cana, empregando sistemas de análise por injeção em fluxo com o uso de DNS

Determinação a baixo custo de açúcares redutores totais em caldo-de-cana, empregando sistema de análise por injeção em fluxo com o uso de DNS Um sistema de análise por injeção em fluxo foi utilizado para a determinação de açúcares redutores totais em caldo-de-cana. O método é baseado na hidrólise da sacarose, seguido da oxidação dos açúcares redutores pelo ácido 3,5-dinitrosalicílico (DNS) em meio alcalino, e determinação espectrofotométrica em 510 nm. Visando obter melhor sensibilidade e seletividade, os parâmetros volume de amostra e comprimento dos reatores foram estudados para avaliar o comportamento das curvas analíticas. Foram utilizados mini-compressores de aquários no lugar de bomba peristálticas e cela espectrofotométrica em acrílico no lugar de cela de vidro importada, a fim de minimizar o consumo de reagentes e o custo do sistema FIA. O presente sistema foi comparado ao método Lane-Eynon recomendado pelo Ministério da Agricultura. Usando o teste-t, não foram constatadas diferenças significativas entre os resultados dos dois métodos, sendo que os desvios relativos foram ao redor de 1%. O método permite analisar cerca de 14 amostras h-1 com desvio padrão relativo inferior a 1,35%.