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.

On-line determination of Sb(III) and total Sb using baker's yeast immobilized on polyurethane foam and hydride generation inductively coupled plasma optical emission spectrometry

The yeast Saccharomyces cerevisiae was immobilized in cubes of polyurethane foam and the ability of this immobilized material to separate Sb(III) and Sb(V) was investigated. A method based on sequential determination of total Sb (after on-line reduction of Sb(V) to Sb(III) with thiourea) and Sb(Ill) (after on-line solid-liquid phase extraction) by hydride generation inductively coupled plasma optical emission spectrometry is proposed. A flow system assembled with solenoid valves was used to manage all stages of the process. The effects of pH, sample loading and elution flow rates on solid-liquid phase extraction of Sb(III) were evaluated. Also, the parameters related to online pre-reduction (reaction coil and flow rates) were optimized. Detection limits of 0.8 and 0.15 mu g L-1 were obtained for total Sb and Sb (III), respectively. The proposed method was applied to the analysis of river water and effluent samples. The results obtained for the determination of total Sb were in agreement with expected values, including the river water Standard Reference Material 1640 certified by the National Institute of Standards and Technology (NIST). Recoveries of Sb(III) and Sb(V) in spiked samples were between 81 19 and I I I 15% when 120 s of sample loading were used. (c) 2006 Elsevier B.V. All rights reserved.

Speciation analysis of Sn(II) and Sn(IV) using baker's yeast and inductively coupled plasma optical emission spectrometry

The use of Saccharomyces cerevisiae as a substrate to selectively retain Sn(II) and Sn(IV) has been investigated. Several factors affecting the retention of the analytes by yeast, such as pH, amount of biomass, temperature and time of contact were evaluated. Based on this study, a method for determination of Sn(II) and Sn(IV) combining inductively coupled plasma optical emission spectrometry (ICP OES) and solid phase extraction using Saccharomyces cerevisiae is proposed. The procedure consists of the selective retention of Sn(IV) by yeast at pH = 2.0 while Sn(II) remains in solution. Determination of tin in the solid phase was easily carried out by submitting a slurry of the yeast (0.5 g/40 mL) directly to ICP OES. The precision of the extraction procedure was characterized by an RSD lower than 4%. The detection limits of tin (3 sigma) in the solid phase and the liquid phase were 1.1 and 0.7 mu g L-1, respectively. The proposed approach was evaluated for determination of Sn(II) and Sn(IV) in spiked river water and real samples of industrial waste water (untreated and treated). For all samples, recoveries of spiked Sn(II) and Sn(IV) were between 85 and 112%.

Determination of Cd(II) and Cd-metallothioneins in biological extracts using baker's yeast and inductively coupled plasma optical emission spectrometry

The use of Saccharomyces cerevisiae as a sorbent material to separate Cd(II) and Cd-metallothionein complex (Cd-MT) has been explored. Solid-liquid phase extractions were carried out in batch mode and the main parameters of the process (pH, temperature, time of incubation, amount of biomass and analyte) were evaluated. Under optimized conditions, the yeast quantitatively retain (94 +/- 5%) the Cd(II) while 97 +/- 2% of the Cd-MT remain in the supernatant. on base of the findings of this study, a simple method is proposed to determine Cd(II) and Cd-MT in cytosols extracted from mouse kidney and crab hepatopancreas. Inductively coupled plasma optical emission spectrometry was used to quantify the analytes in solid and liquid phase. Determination of Cd in the solid phase was carried out by introducing a slurry of the yeast (0.0625 g/10 mL) directly to the inductively coupled plasma optical emission spectrometer. Mixed standards solutions, which also have been submitted to the extraction procedure, were used to quantify the analytes in the samples. Thus, matrix effects due to nebulization of the slurry were overcame. Limits of detection (3 sigma) for Cd(II) and Cd-MT were 1.5 and 1.2 mu g L-1, respectively. Relative standard deviations of signals were 4.2% for measurements in the slurry of solid phase and 2.1% for measurements in the liquid phase. Recoveries of the analytes in cytosol samples were between 76 and 114%. The concentrations of Cd(II) (2.4 +/- 0.5 mu g L-1) and Cd-MT (3.0 +/- 0.5 mu g L-1) found by using the proposed approach were close to those found by tangential-flow ultrafiltration technique (2.6 +/- 0.7 mu g L-1 for Cd(II) and 3.7 +/- 1.7 mu g L-1 for Cd-MT).

The use of silica-immobilized brown alga (Pilayella littoralis) for metal preconcentration and determination by inductively coupled plasma optical emission spectrometry

The brown alga Pilayella littoralis was used as a new biosorbent in an on-line metal preconcentration procedure in a flow-injection system. Al, Co, Cu and Fe were determined in lake water samples by inductively coupled plasma optical emission spectrometry (ICP-OES) after preconcentration in a silica-immobilized alga column. Like other algae, P. littoralis exhibited strong affinity for these metals proving to be an effective accumulation medium. Metals were bound at pH 5.5 and were displaced at pH < 2 with diluted HCl. The enrichment factors for Cu-II, Fe-III, Al-III and Co-II were 13, 7, 16 and 11, respectively. Metal sorption efficiency ranged from 86 to 90%. The method accuracy was assessed by using drinking water certified reference material and graphite furnace atomic absorption spectrometry (GFAAS) as a comparison technique. The column procedure allowed a less time consuming, easy regeneration of the biomaterial and rigidity of the alga provided by its immobilization on silica gel. (C) 2003 Elsevier B.V. All rights reserved.

Analysis of cement slurries by inductively coupled plasma optical emission spectrometry with axial viewing

The feasibility of Portland cement analysis by introduction of slurries in an inductively coupled plasma optical emission spectrometer (ICP-OES) with axial viewing has been evaluated. After a fast manual grinding of the cement samples, owing to the pulverized state of this material, 0.1% m/v slurries were prepared in 1% v/v HCl. The calibration was performed adopting two strategies: one based on slurries prepared from different masses (50, 75, 100 and 125 mg) of a Portland cement standard reference material (NIST SRM 1881), and the other one based on aqueous reference solutions. A complete analysis of cement for major (Al, Ca, Fe, Mg and Si), minor and trace elements (Mn, P, S, Sr and Ti) was accomplished. Both strategies led to accurate results for commercial Portland cement samples, except for Si and Ti. for which the calibration with aqueous reference solutions resulted in low values. Applying a paired t-test it was shown that most results were in agreement at a 95% confidence level with a conventional fusion decomposition procedure. The ICP-OES with axial viewing and end-on gas configuration for removal of the recombination plasma zone was effective for cement slurry analysis without any undesirable particle deposition in the pre-optics interface and without severe spectral interferences. (C) 2002 Elsevier B.V. B.V. All rights reserved.

On-line redox speciation analysis of antimony using L-proline immobilized on controlled pore glass and hydride generation inductively coupled plasma optical emission spectrometry for detection

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

Ion balance in waters through inductively coupled plasma optical emission spectrometry

Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) has been employed to carry out the determination of both major anions and cations in water samples. The anion quantification has been performed by means of a new automatic accessory. In this device chloride has been determined by continuously adding a silver nitrate solution. As a result solid silver chloride particles are formed and retained on a nylon filter inserted in the line. The emission intensity is read at a silver characteristic wavelength. By plotting the drop in silver signal versus the chloride concentration, a straight line is obtained. As regards bicarbonate, this anion has been on-line transformed into carbon dioxide with the help of a 2.0 mol L−1 nitric acid stream. Carbon signal is linearly related with bicarbonate concentration. Finally, information about sulfate concentration has been achieved by means of the measurement of sulfur emission intensity. All the steps have been simultaneously and automatically performed. With this setup detection limits have been 1.0, 0.4 and 0.09 mg L−1 for chloride, bicarbonate and sulfate, respectively. Furthermore, it affords good precision with RSD below 6 %. Cation (Ca, Mg, Na and K) concentration, in turn, has been obtained by simultaneously reading the emission intensity at characteristic wavelengths. The obtained limits of detection have been 8 × 10−3, 2 × 10−3, 8 × 10−4 and 10−2 mg L−1 for sodium, potassium, magnesium and calcium, respectively. As regards sample throughput, about 30 samples h−1 can be analysed. Validation results have revealed that the obtained concentrations for these anions are not significantly different as compared to the data provided by conventional methods. Finally, by considering the data for anions and cations, precise ion balances have been obtained for well and mineral water samples.

IMPROVED SAMPLE INTRODUCTION SYSTEMS FOR INDUCTIVELY COUPLED PLASMA OPTICAL EMISSION SPECTROMETRY AND THEIR APPLICATION TO THE ANALYSIS OF SIMPLE AND COMPLEX MATRICES

The objective of this thesis is to explore new and improved methods for greater sample introduction efficiency and enhanced analytical performance with inductively coupled plasma optical emission spectrometry (ICP-OES). Three projects are discussed in which the capabilities and applications of ICP-OES are expanded: 1. In the first project, a conventional ultrasonic nebuliser was modified to replace the heater/condenser with an infrared heated pre-evaporation tube. In continuation from previous works with pre-evaporation, the current work investigated the effects of heating with infrared block and rope heaters on two different ICP-OES instruments. Comparisons were made between several methods and setups in which temperatures were varied. By monitoring changes to sensitivity, detection limit, precision, and robustness, and analyzing two certified reference materials, a method with improved sample introduction efficiency and comparable analytical performance to a previous method was established. 2. The second project involved improvements to a previous work in which a multimode sample introduction system (MSIS) was modified by inserting a pre-evaporation tube between the MSIS and torch. The new work focused on applying an infrared heated ceramic rope for pre-evaporation. This research was conducted in all three MSIS modes (nebulisation mode, hydride generation mode, and dual mode) and on two different ICP-OES instruments, and comparisons were made between conventional setups in terms of sensitivity, detection limit, precision, and robustness. By tracking both hydride-forming and non-hydride forming elements, the effects of heating in combination with hydride generation were probed. Finally, optimal methods were validated by analysis of two certified reference materials. 3. A final project was completed in collaboration with ZincNyx Energy Solutions. This project sought to develop a method for the overall analysis of a 12 M KOH zincate fuel, which is used in green energy backup systems. By employing various techniques including flow injection analysis and standard additions, a final procedure was formulated for the verification of K concentration, as well as the measurement of additives (Al, Fe, Mg, In, Si), corrosion products (such C from CO₃²¯), and Zn particles both in and filtered from solution. Furthermore, the effects of exposing the potassium zincate electrolyte fuel to air were assessed.

Determination of Nb and Ta in Nb/Ta minerals by inductively coupled plasmas optical emission spectrometry using slurry sample introduction

The determination of Nb and Ta in Nb-Ta minerals was accomplished by slurry nebulization inductively coupled plasma optical emission spectrometry (ICP-OES), using a clog-free V-groove ceramic nebulizer. Samples were first wet-ground to appropriate particle sizes with narrow size distribution and 90% of the particles in the slurry were smaller than 2.32 mu m in diameter. Subsamples were then dispersed in pH 9 aqueous solutions, and agitated in an ultrasonic bath for 15 min prior to analysis. Due to the lack of slurry standards matching well with the samples, calibration was simply carried out using aqueous solution standards. Results were compared with those obtained from a conventional fusion decomposition procedure and acid digestion procedures and a good agreement between the measured and referred values was obtained. The technique provided a good alternative for the rapid determination of Nb and/or Ta in their corresponding minerals.

ON THE SIGNIFICANCE OF WAVELENGTH POSITIONING ACCURACY IN MULTICOMPONENT ANALYSIS TECHNIQUES FOR THE CORRECTION OF LINE INTERFERENCES IN INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION-SPECTROMETRY

The present paper reports some definite evidence for the significance of wavelength positioning accuracy in multicomponent analysis techniques for the correction of line interferences in inductively coupled plasma atomic emission spectrometry (ICP-AES). Using scanning spectrometers commercially available today, a large relative error, DELTA(A) may occur in the estimated analyte concentration, owing to wavelength positioning errors, unless a procedure for data processing can eliminate the problem of optical instability. The emphasis is on the effect of the positioning error (deltalambda) in a model scan, which is evaluated theoretically and determined experimentally. A quantitative relation between DELTA(A) and deltalambda, the peak distance, and the effective widths of the analysis and interfering lines is established under the assumption of Gaussian line profiles. The agreement between calculated and experimental DELTA(A) is also illustrated. The DELTA(A) originating from deltalambda is independent of the net analyte/interferent signal ratio; this contrasts with the situation for the positioning error (dlambda) in a sample scan, where DELTA(A) decreases with an increase in the ratio. Compared with dlambda, the effect of deltalambda is generally less significant.

A new closed-vessel conductively heated digestion system: fostering plant analysis by inductively coupled plasma optical emission spectroscopy

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

Characteristics in frequency domain by inductively coupled plasma atomic emission spectrometry with charge injection detection

The charactesistics of two-dimension spectra obtained by inductively coupled plasma atomic emission spectrometry (ICP-AES) with charge injection detection (CID) in frequency domain were studied in the present paper. The measurement spectra were Fourier transformed and the frequency distribution of the spectra was obtained. Results showed that the spectra in frequency domain could he divided into two parts:high frequency and low frequency signals. The later stood for measurement spectra and the former for background and noises. However, the high frequecny signals could not be smoothed simply to reduce noises because the background was deteriorated even though the spectral signal did not change significantly.

Factor analysis used to peak position optimization and spectral interference correction in inductively coupled plasma atomic emission spectrometry

Target transformation factor analysis was used to correct spectral interference in inductively coupled plasma atomic emission spectrometry (ICP-BES) for the determination of rare earth impurities in high purity thulium oxide. Data matrix was constructed with pure and mixture vectors and background vector. A method based on an error evaluation function was proposed to optimize the peak position, so the influence of the peak position shift in spectral scans on the determination was eliminated or reduced. Satisfactory results were obtained using factor analysis and the proposed peak position optimization method.