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.

Evaluation of the use of multiple lines for determination of metals in water by inductively coupled plasma optical emission spectrometry with axial viewing

Inductively coupled plasma optical emission spectrometers (ICP DES) allow fast simultaneous measurements of several spectral lines for multiple elements. The combination of signal intensities of two or more emission lines for each element may bring such advantages as improvement of the precision, the minimization of systematic errors caused by spectral interferences and matrix effects. In this work, signal intensities for several spectral lines were combined for the determination of Al, Cd, Co, Cr, Mn, Pb, and Zn in water. Afterwards, parameters for evaluation of the calibration model were calculated to select the combination of emission lines leading to the best accuracy (lowest values of PRESS-Predicted error sum of squares and RMSEP-Root means square error of prediction). Limits of detection (LOD) obtained using multiple lines were 7.1, 0.5, 4.4, 0.042, 3.3, 28 and 6.7 mu g L(-1) (n = 10) for Al, Cd. Co, Cr, Mn, Pb and Zn, respectively, in the presence of concomitants. On the other hand, the LOD established for the most intense emission line were 16. 0.7, 8.4, 0.074. 23, 26 and 9.6 mu g L(-1) (n = 10) for these same elements in the presence of concomitants. The accuracy of the developed procedure was demonstrated using water certified reference material. The use of multiple lines improved the sensitivity making feasible the determination of these analytes according to the target values required for the current environmental legislation for water samples and it was also demonstrated that measurements in multiple lines can also be employed as a tool to verify the accuracy of an analytical procedure in ICP DES. (C) 2009 Elsevier B.V. All rights reserved.

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.

Determination of heavy metals by inductively coupled plasma-optical emission spectrometry in fish from the Piracicaba River in Southern Brazil

A total of 202 fish, representing 16 species, were collected during 2008 (March-October) in the Tanquan region of the Piracicaba River using nets. Flesh samples were collected and analyzed, using inductively coupled plasma-optical emission spectroscopy for Al, As, Cd, Co Cr, Cu, Mn, Mo, Ni, Ph, Se, Sn, Sr, and Zn. The results showed that the flesh of these fish all contained extremely high levels of Al and Sr, and moderately high levels of Cr, As, Zn, Ni. Mn and Pb. The metals were higher in these fish during rainy season, with fish collected during the months of March and October being the highest. In addition, the accumulation of metals was species-dependent. Cascudos (Hypostomus punctatus) and piranhas (Serrasalmus spilopleura) exhibited high levels of almost all of the metals, while curimbata (Prochilodus lineatus) had moderate levels. A few species, including pacu (Piaractus mesopotamicus) and dourado (Salminus maxillosus), had very low levels of most metals. The results show that the Piracicaba River Basin is widely contaminated with high levels of many toxic heavy metals, and that human consumption of some fish species is a human health concern. (C) 2009 Elsevier B.V. All rights reserved.

A method for Ca, Fe, Ga, Na, Si and Zn determination in alumina by inductively coupled plasma optical emission spectrometry after aluminum precipitation

In this present work a method for the determination of Ca, Fe, Ga, Na, Si and Zn in alumina (Al(2)O(3)) by inductively coupled plasma optical emission spectrometry (ICP OES) with axial viewing is presented. Preliminary studies revealed intense aluminum spectral interference over the majority of elements and reaction between aluminum and quartz to form aluminosilicate, reducing drastically the lifetime of the torch. To overcome these problems alumina samples (250 mg) were dissolved with 5 mL HCl + 1.5 mLH(2)SO(4) + 1.5 mL H(2)O in a microwave oven. After complete dissolution the volume was completed to 20 mL and aluminum was precipitated as Al(OH)(3) with NH(3) (by bubbling NH(3) into the solution up to a pH similar to 8, for 10 min). The use of internal standards (Fe/Be, Ga/Dy, Zn/In and Na/Sc) was essential to obtain precise and accurate results. The reliability of the proposed method was checked by analysis of alumina certified reference material (Alumina Reduction Grade-699, NIST). The found concentrations (0.037%w(-1) CaO, 0.013% w w(-1) Fe(2)O(3), 0.012%w w(-1)Ga(2)O(3), 0.49% w w(-1) Na(2)O, 0.014% w w(-1) SiO(2) and 0.013% w w(-1) ZnO) presented no statistical differences compared to the certified values at a 95% confidence level. (C) 2011 Elsevier B.V. All rights reserved.

Evaluation of laser induced breakdown spectrometry for the determination of macro and micronutrients in pharmaceutical tablets

The aim of this work is to demonstrate the feasibility of laser induced breakdown spectrometry (LIBS) for the determination of macro and micronutrients in multielement tablets. The experimental setup was designed by using a laser Q-switch (Nd:YAG, 10 Hz, lambda = 1064 nm) and the emission signals were collected by lenses into an optical fiber coupled to an echelle spectrometer equipped with a high-resolution intensified charge coupled device (ICCD). Tablets were cryogenically ground and thereafter pelletized before LIBS analysis. Calibration curves were made by employing samples and mixtures of commercial multielement tablets with binders at different ratios. Best results were achieved by using the following experimental conditions: 29 J cm(-2) laser fluence, 165 mm lens to sample distance (f = 200 mm), 2.0 mu s delay time, 5.0 mu s integration time and 5 accumulated laser pulses. In general, the results obtained by the proposed LIBS procedure were in agreement with those obtained by ICP OES from the corresponding acid digests and coefficients variation of LIBS measurements varied from 2 to 16%. The metrological figures of merit indicate that LIBS fits for the intended purposes, and can be recommended for the analysis of multielement tablets and similar matrices aiming the determination of Ca, Cu, Fe, Mg, Mn, P and Zn.

Preliminary studies of laser-induced breakdown spectrometry for the determination of Ba, Cd, Cr and Pb in toys

The performance of laser-induced breakdown spectrometry (LIBS) for the determination of Ba, Cd, Cr and Pb in toys has been evaluated by using a Nd:YAG laser operating at 1064 nm and an Echelle spectrometer with intensified charge-coupled device detector. Samples were purchased in different cities of Sao Paulo State market and analyzed directly without sample preparation. Laser-induced breakdown spectrometry experimental conditions (number of pulses, delay time. integration time gate and pulse energy) were optimized by using a Doehlert design. Laser-induced breakdown spectrometry signals correlated reasonably well with inductively coupled plasma optical emission spectrometry (ICP OES) concentrations after microwave-assisted acid digestion of selected samples. Thermal analysis was used for polymer identification and scanning electron microscopy to Visualize differences in crater geometry of different polymers employed for toy fabrication. Results indicate that laser-induced breakdown spectrometry can be proposed as a rapid screening method for investigation of potentially toxic elements in toys. The unique application of laser-induced breakdown spectrometry for identification of contaminants in successive layers of ink and polymer is also demonstrated. (C) 2009 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.

Simultaneous determination of chromium and manganese in alumina by slurry sampling graphite furnace atomic absorption spectrometry using NbC and NaF as modifiers

This paper reports a method for the direct and simultaneous determination of Cr and Mn in alumina by slurry sampling graphite furnace atomic absorption spectrometry (SiS-SIMAAS) using niobium carbide (NbC) as a graphite platform modifier and sodium fluoride (NaF) as a matrix modifier. 350 mu g of Nb were thermally deposited on the platform surface allowing the formation of NbC (mp 3500 degrees C) to minimize the reaction between aluminium and carbon of the pyrolytic platform, improving the graphite tube lifetime up to 150 heating cycles. A solution of 0.2 mol L(-1) NaF was used as matrix modifier for alumina dissolution as cryolite-based melt, allowing volatilization during pyrolysis step. Masses (c.a. 50 mg) of sample were suspended in 30 ml of 2.0% (v/v) of HNO(3). Slurry was manually homogenized before sampling. Aliquots of 20 mu l of analytical solutions and slurry samples were co-injected into the graphite tube with 20 mu l of the matrix modifier. In the best conditions of the heating program, pyrolysis and atomization temperatures were 1300 degrees C and 2400 degrees C, respectively. A step of 1000 degrees C was optimized allowing the alumina dissolution to form cryolite. The accuracy of the proposed method has been evaluated by the analysis of standard reference materials. The found concentrations presented no statistical differences compared to the certified values at 95% of the confidence level. Limits of detection were 66 ng g(-1) for Cr and 102 ng g(-1) for Mn and the characteristic masses were 10 and 13 pg for Cr and Mn, respectively.

Mineralogical characterization of a highly-weathered soil by the Rietveld Method

The mineralogical characterization through mineral quantification of Brazilian soils by X-ray diffraction data using the Rietveld Method is not common. A mineralogical quantification of an Acric Ferralsol from the Ponta Grossa region, state of Paraná, Brazil, was carried out using this Method with X-Ray Diffraction data to verify if this method was suitable for mineral quantification of a highly-weathered soil. The A, AB and B3 horizons were fractioned to separate the different particle sizes: clay, silt, fine sand (by Stokes Law) and coarse sand fractions (by sieving), with the procedure free of chemical treatments. X-ray Fluorescence, Inductively Coupled Plasma Atomic Emission Spectrometry, Infrared Spectroscopy and Mössbauer Spectroscopy were used in order to assist the mineral identification and quantification. The Rietveld Method enabled the quantification of the present minerals. In a general way, the quantitative mineralogical characterization by the Rietveld Method revealed that quartz, gibbsite, rutile, hematite, goethite, kaolinite and halloysite were present in the clay and silt fractions of all horizons. The silt fractions of the deeper horizons were different from the more superficial ones due to the presence of large amounts of quartz. The fine and the coarse sand fractions are constituted mainly by quartz. Therefore, a mineralogical quantification of the finer fraction (clay and silt) by the Rietveld Method was successful.

Distinção entre cachaças destiladas em alambiques e em colunas usando quimiometria

One hundred fifteen cachaça samples derived from distillation in copper stills (73) or in stainless steels (42) were analyzed for thirty five itens by chromatography and inductively coupled plasma optical emission spectrometry. The analytical data were treated through Factor Analysis (FA), Partial Least Square Discriminant Analysis (PLS-DA) and Quadratic Discriminant Analysis (QDA). The FA explained 66.0% of the database variance. PLS-DA showed that it is possible to distinguish between the two groups of cachaças with 52.8% of the database variance. QDA was used to build up a classification model using acetaldehyde, ethyl carbamate, isobutyl alcohol, benzaldehyde, acetic acid and formaldehyde as chemical descriptors. The model presented 91.7% of accuracy on predicting the apparatus in which unknown samples were distilled.

Determination and fractionation of barium in Brazil nuts

Several sample preparation strategies were employed for determination and fractionation of barium in Brazil nuts using measurements by graphite furnace atomic absorption spectrometry (GF AAS) and inductively coupled plasma optical emission spectrometry with axial view (ICP OES). This food is widely consumed because of its nutritional value and good taste. The chemical analysis of Brazil nuts is not trivial due to their complex matrix. The fractionation of barium in Brazil nuts was studied owing to the toxicity of this element and the strong correlation between chemical form and absorption. Total concentrations of barium varied from 860 to 2084 mg kg-1. Sequential extractions were performed based on solubility in different media and also according to lipids, proteins and low molecular weight fractions (LMW). The greatest contents of barium were determined in the LMW and in the water insoluble fractions with concentrations in the range 778 to 1606 and 551 to 1520 mg kg-1, respectively. Based on these results it can be inferred that Ba is not absorbed when Brazil nuts are ingested. Considering both the contents of barium and sulfur in different fractions and stoichiometric calculations it was also possible to assume that barium occurs mainly in the BaSO4 form. The presence of this chemical form was also confirmed by thermogravimetric measurements.

Association of dental enamel lead levels with risk factors for environmental exposure

OBJECTIVE: To analyze household risk factors associated with high lead levels in surface dental enamel. METHODS: A cross-sectional study was conducted with 160 Brazilian adolescents aged 14-18 years living in poor neighborhoods in the city of Bauru, southeastern Brazil, from August to December 2008. Body lead concentrations were assessed in surface dental enamel acid-etch microbiopsies. Dental enamel lead levels were measured by graphite furnace atomic absorption spectrometry and phosphorus levels were measured by inductively coupled plasma optical emission spectrometry. The parents answered a questionnaire about their children's potential early (05 years old) exposure to well-known lead sources. Logistic regression was used to identify associations between dental enamel lead levels and each environmental risk factor studied. Social and familial covariables were included in the models. RESULTS: The results suggest that the adolescents studied were exposed to lead sources during their first years of life. Risk factors associated with high dental enamel lead levels were living in or close to a contaminated area (OR = 4.49; 95% CI: 1.69;11.97); and member of the household worked in the manufacturing of paints, paint pigments, ceramics or batteries (OR = 3.43; 95% CI: 1.31;9.00). Home-based use of lead-glazed ceramics, low-quality pirated toys, anticorrosive paint on gates and/or sale of used car batteries (OR = 1.31; 95% CI: 0.56;3.03) and smoking (OR = 1.66; 95% CI: 0.52;5.28) were not found to be associated with high dental enamel lead levels. CONCLUSIONS: Surface dental enamel can be used as a marker of past environmental exposure to lead and lead concentrations detected are associated to well-known sources of lead contamination.

Characterization of aqueous silver nitrate solutions for leakage tests

OBJECTIVE: To determine the pH over a period of 168 h and the ionic silver content in various concentrations and post-preparation times of aqueous silver nitrate solutions. Also, the possible effects of these factors on microleakage test in adhesive/resin restorations in primary and permanent teeth were evaluated. MATERIAL AND METHODS: A digital pHmeter was used for measuring the pH of the solutions prepared with three types of water (purified, deionized or distilled) and three brands of silver nitrate salt (Merck, Synth or Cennabras) at 0, 1, 2, 24, 48, 72, 96 and 168 h after preparation, and storage in transparent or dark bottles. Ionic silver was assayed according to the post-preparation times (2, 24, 48, 72, 96, 168 h) and concentrations (1, 5, 25, 50%) of solutions by atomic emission spectrometry. For each sample of each condition, three readings were obtained for calculating the mean value. Class V cavities were prepared with enamel margins on primary and permanent teeth and restored with the adhesive systems OptiBond FL or OptiBond SOLO Plus SE and the composite resin Filtek Z-250. After nail polish coverage, the permanent teeth were immersed in 25% or 50% AgNO3 solution and the primary teeth in 5% or 50% AgNO3 solutions for microleakage evaluation. ANOVA and the Tukey's test were used for data analyses (α=5%). RESULTS: The mean pH of the solutions ranged from neutral to alkaline (7.9±2.2 to 11.8±0.9). Mean ionic silver content differed depending on the concentration of the solution (4.75±0.5 to 293±15.3 ppm). In the microleakage test, significant difference was only observed for the adhesive system factor (p=0.000). CONCLUSIONS: Under the tested experimental conditions and based on the obtained results, it may be concluded that the aqueous AgNO3 solutions: have neutral/alkaline pH and service life of up to 168 h; the level of ionic silver is proportional to the concentration of the solution; even at 5% concentration, the solutions were capable of indicating loss of marginal seal in the composite restorations; the 3-step conventional adhesive system had better performance regarding microleakage in enamel on primary and permanent teeth.

Composição química dos frutos de Campomanesia xanthocarpa Berg-Myrtaceae

Frutos in natura de C. xanthocarpa (Myrtaceae), coletados em diferentes estádios de amadurecimento na Floresta Estadual de Assis, município de Assis - SP, foram avaliados por meio de métodos tradicionais de análise, técnicas cromatográficas e de espectrometria de massas e de emissão ótica quanto à composição nutricional, ao perfil químico do óleo volátil e ao teor de elementos inorgânicos. Os resultados mostraram alto teor de água (81,4%); lipídios (1,9%); carboidratos totais (8,9%); fibra alimentar (6,3%); além de quantidades razoáveis de ácido ascórbico (17,8 mg.100 g-1); e traços de riboflavina (0,09 mg.100 g-1). No óleo volátil (0,2%), pôde-se identificar 62 componentes, correspondendo a 100% dos constituintes do óleo, destacando-se dentre eles os monoterpenos α-pineno (15%), o-cimeno (10,8%), β-pineno (10,5%). Entre os minerais (16), os principais elementos foram o K (2084 mg.kg-1), P (149 mg.kg-1), Mg (135 mg.kg-1) e, como microelementos, o Fe (6,4 mg.kg-1), Cu (93,3 mg.100 g-1) e Pb (1,3 mg.kg-1). O valor energético do fruto (57,3 kcal.100 g-1) deve-se quase que exclusivamente aos teores de carboidratos totais (8,9%).