Simultaneous preconcentration of copper, zinc, cadmium, and nickel in water samples by cloud point extraction using 4-(2-pyridylazo)-resorcinol and their determination by inductively coupled plasma optic emission spectrometry

A procedure for simultaneous separation/preconcentration of copper. zinc, cadmium, and nickel in water samples, based on cloud point extraction (CPE) as a prior step to their determination by inductively coupled plasma optic emission spectrometry (ICP-OES), has been developed. The analytes reacted with 4-(2-pyridylazo)-resorcinol (PAR) at pH 5 to form hydrophobic chelates, which were separated and preconcentrated in a surfactant-rich phase of octylphenoxypolyethoxyethanol (Triton X-I 14). The parameters affecting the extraction efficiency of the proposed method, such as sample pH, complexing agent concentration, buffer amount, surfactant concentration, temperature, kinetics of complexation reaction, and incubation time were optimized and their respective values were 5, 0.6 mmol L(-1). 0.3 mL, 0.15% (w/v), 50 degrees C, 40 min, and 10 min for 15 mL of preconcentrated solution. The method presented precision (R.S.D.) between 1.3% and 2.6% (n = 9). The concentration factors with and without dilution of the surfactant-rich phase for the analytes ranged from 9.4 to 10.1 and from 94.0 to 100.1, respectively. The limits of detection (L.O.D.) obtained for copper, zinc, cadmium, and nickel were 1.2, 1.1, 1.0. and 6.3 mu g L(-1), respectively. The accuracy of the procedure was evaluated through recovery experiments on aqueous samples. (C) 2009 Published by Elsevier B.V.

Sources of particulate matter: emission profile of biomass burning

Biomass burning is an important source of atmospheric Particulate Matter (PM) in Brazil: the burning of forests in the northwest and of sugar cane plantations in the southeast are important examples. The objective of this work is the measurement of the PM emission profile of burning of sugar cane and other characteristic vegetative burning in the region of Sao Carlos-SP/Brazil. Samples of PM(10) and PM(2.5) were collected in different conditions, including small laboratory controlled burnings and real ones. The samples were analysed by X-Ray Fluorescence (XRF) and 14 chemical elements quantified. t-Student tests were performed to compare the obtained profiles, using as a reference a vegetative burn profile taken from the USEPA data bank SPECIATE. All measured profiles presented significant amounts of Cl and K, which are confirmed as tracers of sugar cane foliage burning.

A critical evaluation of a flow-cell based on a liquid core waveguide for chemiluminescence measurements

Liquid-core waveguides (LCWs), devices that constrain the emitted radiation minimizing losses during the transport, are an alternative to maximize the amount of detected radiation in luminescence. In this work, the performance of a LCW flow-cell was critically evaluated for chemiluminescence measurements, by using as model the oxidation of luminol by hydrogen peroxide or hypochlorite. An analytical procedure for hypochlorite determination was also developed, with linear response in the range 0.2-3.8 mg/L (2.7-51 mu mol/L), a detection limit estimated as 8 mu g/L (0.64 mu mol/L) at the 99.7% confidence level and luminol consumption of 50 mu g/determination. The coefficients of variation were 3.3% and 1.6% for 0.4 and 1.9 mg/L CIO(-), respectively, with a sampling rate of 164 determinations/h. The procedure was applied to the analysis of Dakin`s solution samples, yielding results in agreement with those obtained by iodometric titration at the 95% confidence level. Copyright (c) 2008 John Wiley & Sons, Ltd.

A critical evaluation of a long pathlength cell for flow-based spectrophotometric measurements

Coupling of a flow cell based on a liquid core waveguide (LCW) to flow systems for spectro photometric measurements was critically evaluated. Flow-based systems with and without chemical reactions were exploited to estimate the increase in analytical signal in comparison to those obtained with a conventional I cm cell under different experimental conditions. The Schlieren effect associated to intense concentration gradients in the sample zone was investigated with model solutions that do not absorb visible electromagnetic radiation. The effect of radiation scattering was lower than the expected by considering the increase in the optical path, being the magnitude of the perturbation up to 40% higher for the 100-cm LCW cell. Several alternatives for compensation of the Schlieren effect were experimentally investigated. The potentiality of the LCW for turbidimetric measurements and coupling to monosegmented flow analysis was also evaluated. (C) 2008 Elsevier B.V. All rights reserved.

Total carbon measurement in whole tropical soil sample

Soils are an important component in the biogeochemical cycle of carbon, storing about four times more carbon than biomass plants and nearly three times more than the atmosphere. Moreover, the carbon content is directly related on the capacity of water retention, fertility. among other properties. Thus, soil carbon quantification in field conditions is an important challenge related to carbon cycle and global climatic changes. Nowadays. Laser Induced Breakdown Spectroscopy (LIBS) can be used for qualitative elemental analyses without previous treatment of samples and the results are obtained quickly. New optical technologies made possible the portable LIBS systems and now, the great expectation is the development of methods that make possible quantitative measurements with LIBS. The goal of this work is to calibrate a portable LIBS system to carry out quantitative measures of carbon in whole tropical soil sample. For this, six samples from the Brazilian Cerrado region (Argisoil) were used. Tropical soils have large amounts of iron in their compositions, so the carbon line at 247.86 nm presents strong interference of this element (iron lines at 247.86 and 247.95). For this reason, in this work the carbon line at 193.03 nm was used. Using methods of statistical analysis as a simple linear regression, multivariate linear regression and cross-validation were possible to obtain correlation coefficients higher than 0.91. These results show the great potential of using portable LIBS systems for quantitative carbon measurements in tropical soils. (C) 2008 Elsevier B.V. All rights reserved.

Optimization and validation of a LIBS method for the determination of macro and micronutrients in sugar cane leaves

Laser induced breakdown spectrometry (LIBS) was applied for the determination of macro (P, K, Ca, Mg) and micronutrients (B, Cu, Fe, Mn and Zn) in sugar cane leaves, which is one of the most economically important crops in Brazil. Operational conditions were previously optimized by a neuro-genetic approach, by using a laser Nd:YAG at 1064 nm with 110 mJ per pulse focused on a pellet surface prepared with ground plant samples. Emission intensities were measured after 2.0 mu s delay time, with 4.5 mu s integration time gate and 25 accumulated laser pulses. Measurements of LIBS spectra were based on triplicate and each replicate consisted of an average of ten spectra collected in different sites (craters) of the pellet. Quantitative determinations were carried out by using univariate calibration and chemometric methods, such as PLSR and iPLS. The calibration models were obtained by using 26 laboratory samples and the validation was carried out by using 15 test samples. For comparative purpose, these samples were also microwave-assisted digested and further analyzed by ICP OES. In general, most results obtained by LIBS did not differ significantly from ICP OES data by applying a t-test at 95% confidence level. Both LIBS multivariate and univariate calibration methods produced similar results, except for Fe where better results were achieved by the multivariate approach. Repeatability precision varied from 0.7 to 15% and 1.3 to 20% from measurements obtained by multivariate and univariate calibration, respectively. It is demonstrated that LIBS is a powerful tool for analysis of pellets of plant materials for determination of macro and micronutrients by choosing calibration and validation samples with similar matrix composition.

Partial microwave-assisted wet digestion of animal tissue using a baby-bottle sterilizer for analyte determination by inductively coupled plasma optical emission spectrometry

A procedure for partial digestion of bovine tissue is proposed using polytetrafluoroethylene (PTFE) microvessels inside a baby-bottle sterilizer under microwave radiation for multi-element determination by inductively coupled plasma optical emission spectrometry (ICP OES). Samples were directly weighed in laboratory-made polytetrafluoroethylene vessels. Nitric acid and hydrogen peroxide were added to the uncovered vessels, which were positioned inside the baby-bottle sterilizer, containing 500 mL of water. The hydrogen peroxide volume was fixed at 100 mu L The system was placed in a domestic microwave oven and partial digestion was carried out for the determination of Ca, Cu, Fe. Mg, Mn and Zn by inductively coupled plasma optical emission spectrometry. The single-vessel approach was used in the entire procedure, to minimize contamination in trace analysis. Better recoveries and lower residual carbon content (RCC) levels were obtained under the conditions established through a 2(4-1) fractional factorial design: 650 W microwave power, 7 min digestion time, 50 mu L nitric acid and 50 mg sample mass. The digestion efficiency was ascertained according to the residual carbon content determined by inductively coupled plasma optical emission spectrometry. The accuracy of the proposed procedure was checked against two certified reference materials. (C) 2009 Elsevier B.V. All rights reserved.

Simultaneous flow injection preconcentration of lead and cadmium using cloud point extraction and determination by atomic absorption spectrometry

A flow injection (FI) micelle-mediated separation/preconcentration procedure for the determination of lead and cadmium by flame atomic absorption spectrometry (FAAS) has been proposed. The analytes reacted with 1-(2-thiazolylazo)-2-naphthol (TAN) to form hydrophobic chelates, which were extracted into the micelles of 0.05% (w/v) Triton X-114 in a solution buffered at pH 8.4. In the preconcentration stage, the micellar solution was continuously injected into a flow system with four mini-columns packed with cotton, glass wool. or TNT compresses for phase separation. The analytes-containing micelles were eluted from the mini-columns by a stream of 3 mol L(-1) HCl solution and the analytes were determined by FAAS. Chemical and flow variables affecting the preconcentration of the analytes were studied. For 15 mL. of preconcentrated solution, the enhancement factors varied between 15.1 and 20.3, the limits of detection were approximately 4.5 and 0.75 mu g L(-1) for lead and cadmium, respectively. For a solution containing 100 and 10 mu g L(-1) of lead and cadmium, respectively, the R.S.D. values varied from 1.6 to 3.2% (n = 7). The accuracy of the preconcentration system was evaluated by recovery measurements on spiked water samples. The method was susceptible to matrix effects, but these interferences were minimized by adding barium ions as masking agent in the sample solutions, and recoveries from spiked sample varied in the range of 95.1-107.3%. (C) 2008 Elsevier B.V. All rights reserved.

Exploring the emission intensities of ICP OES aided by chemometrics in the geographical discrimination of mineral waters

A rapid method for classification of mineral waters is proposed. The discrimination power was evaluated by a novel combination of chemometric data analysis and qualitative multi-elemental fingerprints of mineral water samples acquired from different regions of the Brazilian territory. The classification of mineral waters was assessed using only the wavelength emission intensities obtained by inductively coupled plasma optical emission spectrometry (ICP OES), monitoring different lines of Al, B, Ba, Ca, Cl, Cu, Co, Cr, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Sb, Si, Sr, Ti, V, and Zn, and Be, Dy, Gd, In, La, Sc and Y as internal standards. Data acquisition was done under robust (RC) and non-robust (NRC) conditions. Also, the combination of signal intensities of two or more emission lines for each element were evaluated instead of the individual lines. The performance of two classification-k-nearest neighbor (kNN) and soft independent modeling of class analogy (SIMCA)-and preprocessing algorithms, autoscaling and Pareto scaling, were evaluated for the ability to differentiate between the various samples in each approach tested (combination of robust or non-robust conditions with use of individual lines or sum of the intensities of emission lines). It was shown that qualitative ICP OES fingerprinting in combination with multivariate analysis is a promising analytical tool that has potential to become a recognized procedure for rapid authenticity and adulteration testing of mineral water samples or other material whose physicochemical properties (or origin) are directly related to mineral content.

Redundancy and Observability Analysis of Conventional and PMU Measurements

This letter shows that the matrix can be used for redundancy and observability analysis of metering systems composed of PMU measurements and conventional measurements (power and voltage magnitude measurements). The matrix is obtained via triangular factorization of the Jacobian matrix. Observability analysis and restoration is carried out during the triangular factorization of the Jacobian matrix, and the redundancy analysis is made exploring the matrix structure. As a consequence, the matrix can be used for metering system planning considering conventional and PMU measurements. These features of the matrix will be outlined and illustrated by numerical examples.

PERMEABILITY MEASUREMENTS OF BRAZILIAN PINUS ELLIOTTII

The liquid and gas phase permeability, of Brazilian Pinus elliotii was studied with a custom built gas and liquid flow rate analysis chamber. The longitudinal gas phase permeability is shown to be six times greater than the radial permeability. There is no statistically significant difference between the longitudinal permeability of water versus wood preservative. Scanning Electron Microscopy (SEM) images confirm that the reported permeability properties arc due to the wood itself rather than to blocked pores or other artifacts of the sample cutting process. Wood composition analysis shows that the samples of Pinus elliotii grown in Brazil are similar to other species of Pinus grown in tropical climates. Specifically, the Pinus elliotti in this study is composed of 17% extractives, 0,27% ashes, 21% hemicellulose, 45% cellulose and 30% lignin. Results arc discussed in the context of the continued search for effective wood preservatives for use in tropical climates.

Laboratory measurements of biomarkers and individual performances in Chironomus xanthus to evaluate pesticide contamination of sediments in a river of southeastern Brazil

This study aimed at evaluating biomarkers, individual and population responses in the native Chironomus xanthus to assess the toxicity of pesticide-contaminated sediments from the Monjolinho River (Southeast Brazil). We measured cholinesterase (ChE) and glutathione S-transferase activities (GST), as biomarkers and survival, individual growth and adult emergence, as individual performances. There was no response of the ChE activity and a tendency to decreased GST activity in contaminated sites, but this was generally not statistically significant. Therefore, there was no association of the biomarker responses with exposure to sediment containing pesticides. In contrast, ash free dry mass was significantly increased and male emergence was decreased in C. xanthus exposed to the same sediments. In conclusion, the selected biomarkers were not sensitive and specific enough to detect and anticipate effects of pesticide contamination at the levels measured in the study area. Nevertheless, individual performances alterations pointed to potential pollution problems and possible ecological consequences. (C) 2010 Elsevier Inc. All rights reserved.

Microstructure and mechanical properties of laser-welded joints of TWIP and TRIP steels

With the aim of investigating a laser-welded dissimilar joint of TWIP and TRIP steel sheets, the microstructure was characterized by means of OM, SEM, and EBSD to differentiate the fusion zone, heat-affected zone, and the base material. OIM was used to differentiate between ferritic, bainitic, and martensitic structures. Compositions were measured by means of optical emission spectrometry and EDX to evaluate the effect of manganese segregation. Microhardness measurements and tensile tests were performed to evaluate the mechanical properties of the joint. Residual stresses and XRD phase quantification were used to characterize the weld. Grain coarsening and martensitic areas were found in the fusion zone, and they had significant effects on the mechanical properties of the weld. The heat-affected zone of the TRIP steel and the corresponding base material showed considerable differences in the microstructure and properties. (C) 2009 Elsevier B.V. All rights reserved.

Experimental analysis of wheel/workpiece dynamic interactions in grinding

The aim of this work is to study the wheel/workpiece dynamic interactions in high-speed grinding using vitrified CBN wheel and DTG (difficult to grind) work materials. This problem is typical in the grinding of engine valve heads. The influence of tangential force per abrasive grain was investigated as an important control variable for the determination of G ratio. Experiments were carried out to observe the influence of vibrations in the wheel wear. The measurements of acoustic emission (AE) and vibration signals helped in identifying the correlation between the dynamic interactions (produced by forced random excitation) and the wheel wear. The wheel regenerative chatter phenomenon was observed by using the wheel mapping technique. (c) 2008 CIRP.

Nondestructive inspection of plastic deformation in commercial carbon steels using magnetic Barkhausen noise

The present work shows measurements of the Magnetic Barkhausen Noise (MBN) in commercial AISI/SAE 1045 and ASTM 36 steel deformed samples. The correlation between the MBN root mean square, Barkhausen signal profile and MBN power spectrum with the plastic deformation is established. The results show that the power spectral density of the Barkhausen signal is more effective as nondestructive evaluator than root mean square of Barkhausen signal. The Outcomes also suggest the presence of unbalanced tensions between the surface and the bulk of sample due to the presence of plastic deformation.