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%.

Mercury speciation in sea food by flow injection cold vapor atomic absorption spectrometry using selective solid phase extraction.

An on-line inorganic and organomercury species separation, preconcentration and determination system consisting of cold vapor atomic absorption spectrometry (CV-AAS or CV-ETAAS) coupled to a flow injection (FI) method was studied. The inorganic mercury species was retained on a column (i.d., 3 mm; length 3 cm) packed to a height of 0.7 cm with a chelating resin aminopropyl-controlled pore glass (550 A) functionalized with [1,5-bis (2 pyridyl)-3-sulphophenyl methylene thiocarbonohydrazyde] placed in the injection valve of a simple flow manifold. Methylmercury is not directly determined. Previous oxidation of the organomercurial species permitted the determination of total mercury. The separation of mercury species was obtained by the selective retention of inorganic mercury on the chelating resin. The difference between total and inorganic mercury determined the organomercury content in the sample. The inorganic mercury was removed on-line from the microcolumn with 6% (m/v) thiourea. The mercury cold vapor generation was performed on-line with 0.2% (m/v) sodium tethrahydroborate and 0.05% (m/v) sodium hydroxide as reducing solution. The determination was performed using CV-AAS and CV-ETAAS, both approaches have been used and compared for the speciation of mercury in sea food. A detection limit of 10 and 6 ng l(-1) was achieved for CV-AAS and CV-ETAAS, respectively. The precision for 10 replicate determinations at the 1 microg l(-1) Hg level was 3.5% relative standard deviation (R.S.D.), calculated from the peak heights obtained. Both approaches were validated with the use of two certified reference materials and by spiking experiments. By analyzing the two biological certified materials, it was evident that the difference between the total mercury and inorganic mercury corresponds to methylmercury. The concentrations obtained by both techniques were in agreement with the certified values or with differences of the certified values for total Hg(2+) and CH(3)Hg(+), according to the t-test for a 95% confidence level. It is amazing how this very simple method is able to provide very important information on mercury speciation.

Quantitative determinations of SiC and SiO2 in new ceramic materials by Fourier transform infrared spectroscopy.

Silicon carbide-based biomorphic ceramics have been fabricated by the pyrolysis and infiltration of natural wood (mukali and pine) with molten silicon. The results of the process of synthesis have been studied in this and other biomorphic ceramics using thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) analysis and scanning electron microscopy (SEM). For evaluating the yield of the synthesis, a new method by Fourier transform infrared spectrometry (FTIR) has been developed for the direct determination of SiC and the simultaneous determination of SiC and SiO2 by absorbance measurements in KBr pellets. The procedure was based on the use of the ratio between the absorbance of the characteristic band of silicon carbide or silica and those of an acetate internal standard added to samples. A multivariate calibration strategy based on inverse least squares and the standard addition approach were employed for quantification. The results obtained for all biomorphic ceramics studied and synthetic samples prepared by mixing pyrolyzed wood with pure SiC were satisfactory. The relative standard deviation for all samples was lower than 2.9%.

Lead ultra-trace on-line preconcentration and determination using selective solid phase extraction and electrothermal atomic absorption spectrometry: applications in seawaters and biological samples.

In this work, a new chelating resin [1,5-bis (2-pyridyl)-3-sulphophenyl methylene] thiocarbonohydrazide immobilised on aminopropyl-controlled pore glass (550 A; PSTH-cpg) was synthesised and packed in a microcolumn which replaced the sample tip of the autosampler arm. The system was applied to the preconcentration of lead. When microliters of 10% HNO3, which acts as elution agent, pass through the microcolumn, the preconcentrated Pb(II) is eluted and directly deposited in a tungsten-rhodium coated graphite tube. With the use of the separation and preconcentration step and the permanent modifiers, the analytical characteristics of the technique were improved. The proposed method has a linear calibration range from 0.012 to 10 ng ml(-1) of lead. At a sample frequency of 36 h(-1) with a 90 s preconcentration time, the enrichment factor was 20.5, the detection and determination limits were 0.012 and 0.14 ng ml(-1), respectively and the precision, expressed as relative standard deviation, was 3.2% (at 1 ng ml(-1)). Results from the determination of Pb in biological certified reference materials were in agreement with the certified values. Seawaters and other biological samples were analysed too.