New magnetic chelating sorbent for chromium speciation by magnetic solid phase extraction on-line with inductively coupled plasma optical emission spectrometry.

A novel sorbent material employing magnetic nanoparticles (MNPs) coupled to graphene oxide (GO) functionalized with 4-aminobenzenesulfonic acid (M@GO-ABS) has been synthesized and applied to develop an inexpensive and automatic method for Cr(III) and Cr(VI) speciation in environmental samples; the developed method combines inductively coupled plasma optical emission spectrometry (ICP-OES) with on-line magnetic solid phase extraction (MSPE). Two magnetic-knotted reactors containing M@GO-ABS were installed in the eight-port injection valve of a flow injection (FI) manifold. Two different eluents were used, one for Cr(VI) (the most toxic chromium species) and one for total Cr concentration. Cr(III) concentration was calculated by the difference between Cr(VI) concentration and total Cr concentration. The optimized method presented detection limits (LOD, peak height) of 0.1 µg L-1 for chromium (VI) and 0.08 µg L-1 for total chromium, and enrichment factors of 15 and 23, respectively. Certified reference materials (TMDA 54.5 fortified lake water and SPS-SW2 surface water) and spiked aqueous samples were used to validate the developed method. The developed method was fruitfully applied to chromium speciation in environmental water samples such as seawater, well water and tap water collected in Málaga (Spain). The obtained values were in good agreement with the certified values, and the recoveries were found in the range of 91-108% for the spiked samples.

Direct solid sampling for speciation of Zn2+ and ZnO nanoparticles in cosmetics by graphite furnace atomic absorption spectrometry.

The application of nanoparticles (NPs) in science and technology is a fast growing field. Therefore, reliable and straightforward analytical methods are required for their fast determination in different types of samples. This work investigates a method that enables the determination of ZnO NPs, discriminating them from ionic zinc in cosmetic samples. The method is based on direct solid sampling high-resolution continuum source electrothermal atomic absorption spectrometry (SS-HR-CS-GFAAS), and has been applied to determination of ZnO NPs, Zn2+ and total Zn in eye shadow samples. In this work the deconvolution of the atomization peak and the calibration by standard additions have been done in order to discriminate and quantify ionic zinc and ZnO NPs. A Zn wavelength with low sensitivity was selected. The proper optimization of the graphite furnace temperature program, minimizing the mineralization of the sample matrix, enables different atomization profiles between the different chemical species of the analyte. Two multiple response surface designs have been used in order to optimize the adequate furnace program to achieve our aims. All the optimization experiments were performed using a sample of eye shadow. Further, a method for the determination of total Zn by direct solid sampling with calibration by aqueous standards, was also optimized. The optimized method was successfully applied to the determination of ionic Zn and ZnO NPs in different eye shadow samples, and has been validated by recovery assays, obtaining recovery percentages between 80 and 125%. Total Zn concentration in the solid samples was validated by the determination of total Zn by direct solid sampling and by the analysis of the same eye shadow samples digested in microwave oven.

Speciation analysis of inorganic arsenic by magnetic solid phase extraction on-line with inductively coupled mass spectrometry determination.

Arsenic, one of the main environmental pollutants and potent natural poison, is a chemical element that is spread throughout the Earth's crust. It is well known that the toxicity of arsenic is highly dependent on its chemical forms. Generally, the inorganic species are more toxic than its organics forms, and As(III) is 60 times more toxic than As(V). In environmental waters, arsenic exists predominantly in two chemical forms: As(III) and As(V). In view of these facts, fast, sensitive, accurate and simple analytical methods for the speciation of inorganic arsenic in environmental waters are required. In this work, a new magnetic solid phase extraction with a hydride generation system was coupled on line with inductively coupled plasma mass spectrometry (MSPE-HG-ICP-MS). The new system was based on the retention of As(III) and As(V) in two knotted reactors filled with (Fe3O4) magnetic nanoparticles functionalized with [1,5-bis (2-pyridyl) 3-sulfophenylmethylene] thiocarbonohydrazide (PSTH-MNPs). As(III) and total inorganic As were sequentially eluted in different reduction conditions. The concentration of As(V) was obtained by subtracting As(III) from total As. The system runs in a fully automated way and the method has proved to have a wide linear range and to be precise, sensitive and fast. The detection limits found were 2.7 and 3.2 ng/L for As(III) and total As, respectively; with relative standard deviations (RSDs) of 2.5% and 2.7% and a sample throughput of 14.4 h-1. In order to validate the developed method, several certified reference samples of environmental waters including sea water, were analyzed and the determined values were in good agreement with the certified values. The proposed method was successfully applied to the speciation analysis of inorganic arsenic in well-water and sea water.

Simultaneous determination of V, Ni and Fe in fuel fly ash using solid sampling high resolution continuum source graphite furnace atomic absorption spectrometry.

A green and simple method has been proposed in this work for the simultaneous determination of V, Ni and Fe in fuel ash samples by solid sampling high resolution continuum source graphite furnace atomic absorption spectrometry (SS HR CS GFAAS). The application of fast programs in combination with direct solid sampling allows eliminating pretreatment steps, involving minimal manipulation of sample. Iridium treated platforms were applied throughout the present study, enabling the use of aqueous standards for calibration. Correlation coefficients for the calibration curves were typically better than 0.9931. The concentrations found in the fuel ash samples analysed ranged from 0.66% to 4.2% for V, 0.23-0.7% for Ni and 0.10-0.60% for Fe. Precision (%RSD) were 5.2%, 10.0% and 9.8% for V, Ni and Fe, respectively, obtained as the average of the %RSD of six replicates of each fuel ash sample. The optimum conditions established were applied to the determination of the target analytes in fuel ash samples. In order to test the accuracy and applicability of the proposed method in the analysis of samples, five ash samples from the combustion of fuel in power stations, were analysed. The method accuracy was evaluated by comparing the results obtained using the proposed method with the results obtained by ICP OES previous acid digestion. The results showed good agreement between them. The goal of this work has been to develop a fast and simple methodology that permits the use of aqueous standards for straightforward calibration and the simultaneous determination of V, Ni and Fe in fuel ash samples by direct SS HR CS GFAAS.

Synthesis and characterization of a novel mesoporous silica functionalized with [1,5 bis(di-2-pyridyl)methylene thiocarbohydrazide] and its application as enrichment sorbent for determination of antimony by FI-HG-ETAAS.

A simple, sensitive, low-cost and rapid flow injection (FI) on-line sorption preconcentration/hydride generation system has been synchronously coupled to an electrothermal atomic absorption spectrometer (ETAAS) for the determination of trace amounts of Sb in aqueous environmental samples (river and sea water samples). The system is based on retention of the analyte onto a micro-column filled with a novel mesoporous silica functionalised with [1,5 bis(di-2-pyridyl) methylene] thiocarbohydrazide placed in the injection valve of the FI manifold. The adsorption capacity of the resin for Sb was found to be 160.8 µmol g(-1). Chemicals and flow variables affecting the continuous preconcentration of antimony, the direct generation of antimony hydride and the final determination of this element by ETAAS were evaluated. The optimized operating conditions selected were: sample pH 5.0, sample flow rate 2.5 ml min(-1), eluent flow rate 5.4 ml min(-1), eluent 2.0% thiourea in 4.0% nitric acid. Under the optimum conditions, the calibration graph obtained was linear over the range 0.025-2.5 µg L(-1). At a sample frequency of 20 h(-1) and 120 s preconcentration time, the enrichment factor was 22. The detection limit of the method (3Æ¡) was 1 ng L(-1) for a 5.0 mL sample volume and the precision was 0.9% (RSD) for 11 replicate determinations at 1.0 µg L(-1) Sb. The preconcentration factor and detection limit can be improved by increasing the preconcentration time, which can be increased at least up to 5 min. The accuracy of the proposed method was demonstrated by analyzing two certified reference materials and by determining the analyte content in spiked environmental water samples. The results obtained using this method were in good agreement with the certified values of the standard reference materials and the recoveries for the spiked river and sea water samples were 91.3-109.9%.

Simultaneous determination of glycols based on fluorescence anisotropy.

Simultaneous determination of non-fluorescent glycols in mixtures without separation or chemical transformation steps is described. Two methods based in the measure of fluorescence anisotropy of a probe such as fluorescein dissolved in the analyte or analyte mixtures are described. In the first method, the anisotropy spectra of pure and mixtures of analytes are used to quantitative determination (if the fluorophor concentration is in a range where fluorescence intensity is proportional to concentration). In the second method, a calibration curve anisotropy-concentration based on the application of the Perrin equation is established. The methods presented here are capable of directly resolving binary mixtures of non-fluorescent glycols on the basis of differences on the fluorescence anisotropy of a fluorescence tracer. Best analytical performances were obtained by application of the method based on Perrin equation. This method is simple, rapid and allows the determination of mixtures of glycols with reasonable accuracy and precision. Detection limits are limited by the quantum yield and anisotropy values of the tracer in the solvents. Recovery values are related to the differences in anisotropy values of the tracer in the pure solvents. Mixtures of glycerine/ethylene glycol (GL/EG), ethylene glycol/1,2-propane diol (EG/1,2-PPD) and polyethylene glycol 400/1,2-propane diol (PEG 400/1,2-PPD) were analysed and recovery values are within 95-120% in the Perrin method. Relative standard deviation are in the range 1.3-2.9% and detection limits in the range 3.9-8.9%.

Modulated anisotropy fluorescence for quantitative determination of carbaryl and benomyl.

Two individual components in mixtures have been resolved by frequency domain fluorescence technique by measuring the observable quantities which characterize the anisotropy decay; differential anisotropy phase and modulated anisotropy ratio (MAR), which in turn are related to the rotational correlation time. The method presented here is capable of directly resolving binaries mixtures of fluorophores on the basis of differences in their rotational diffusion rates. Our results demonstrate that modulation anisotropy ratio measurements can be used for quantitative determination of small analytes, carbaryl and benomyl, having identical or nearly identical fluorescence spectra. This methodology can be applied with good results when the fluorophores have a suitable MAR difference.