Open-tubular capillary electrochromatography for the simultaneous determination of cadmium and copper in plants.

We discuss the separation and determination of cadmium and copper in plant samples such as Triticum durum (wheat) and Helianthus annuus (sunflower) using open tubular capillary electrochromatography with indirect detection. Before performing the analysis, the samples were digested by microwave-assisted methods using HNO3 . Regarding the electrophoretic system, several experimental parameters were previously evaluated such as the capillary surface, mobile phase composition, buffer, pH, and voltage applied. The baseline resolution of the studied metals was obtained within 8 min by using a capillary immobilized with carboxylic multi-walled carbon nanotubes and a background electrolyte composed of 6 mM imidazole, pH 4.0. The applied voltage and the temperature were set at 20 kV and 25°C, respectively. Precision, detection, and quantification limits, along with linearity were investigated. The limits of detection and quantification were 2.20 and 7.40 µg/kg, for Cu2 ⁺ and 0.05 and 0.20 µg/kg in the case of Cd2 ⁺. A good linearity was achieved over a concentration working range of 7.5-100 and 0.2-25 µg/kg for Cu2 ⁺ and Cd2 ⁺ accordingly. Recovery data for validation studies were found in a range of 98.2-101.5% for both analytes.

Development of a FI-HG-ICP-OES solid phase preconcentration system for inorganic selenium speciation in Argentinean beverages.

A preconcentration system has been developed to determine inorganic selenium species. Selenium was retained by a column filled with polyvinyl chloride (PVC) with lanthanum hydroxide co-precipitation. Speciation was achieved by selective photoreduction previous Se preconcentration. The retention pH was optimized at 10.0. Two multivariate calibrations and a central composite design were employed for optimization of the system. Sample, reagents and acid flow rates are significant variables affecting the system. Employing HG-ICP-OES as detection, the optimized system reached a detection limit of 0.03µg/L, and an enhancement factor of 14875 (25 for preconcentration system, 595 for hydride generation). To verify the method' accuracy, two certified reference materials, BCR® 414 Plankton & IRMM-804 Rice Flour, were analysed. The system was applied to inorganic selenium speciation in several Argentinean beverages to estimate their selenium contribution to diet.

Method development for Cd and Hg determination in biodiesel by electrothermal atomic absorption spectrometry with emulsion sample introduction.

A novel method for analysis of biodiesel by electrothermal atomic absorption spectrometry is described. This analytical strategy involves sample preparation as emulsions for routine and reliable determination of Cd and Hg. Several experimental conditions were investigated, including emulsion stability and composition, furnace temperature program and matrix modification. Different calibration strategies were also evaluated, being the analyte addition method preferred both for Cd and Hg. The accuracy was verified through comparison with an acid digestion in a microwave closed system. The injection repeatability was evaluated as the average relative standard deviation (R.S.D %) for five successive firings and was better than 4.4% for Cd and 5.4% Hg respectively. The detection limits, evaluated by the 3σ concept of calculation (n=10), were of 10.2 µg kg(-1) (0.9 µg L(-1)) for Hg and 0.3 µg kg(-1) (0.04 µg L(-1)) for Cd. This method was successfully applied to the determination of Cd and Hg in biodiesel samples obtained from local vendors.

Cloud point extraction for cobalt preconcentration with on-line phase separation in a knotted reactor followed by ETAAS determination in drinking waters.

A novel method for cobalt preconcentration by cloud point extraction with on-line phase separation in a PTFE knotted reactor and further determination by electrothermal atomic absorption spectrometry (ETAAS) is proposed. The cloud point system was formed in the presence of non-ionic micelles of polyethyleneglycolmono-p-nonylphenylether (PONPE 7.5) and it was retained on the inner walls of a knotted reactor (KR). The surfactant rich-phase was removed from the knotted reactor with 75 microL of methanol acidified with 0.8 mol L(-1) nitric acid, directly into the dosing hole of the L'Vov graphite tube. An enrichment factor of 15 was obtained with a preconcentration time of 60 s, with respect to the direct determination of cobalt by ETAAS in aqueous solutions. The value of the detection limit for the preconcentration of 5 mL of sample solution was 10 ng L(-1). The precision, expressed as the relative standard deviation (R.S.D.), for 10 replicate determinations at 0.5 microg L(-1) Co level was 4.5%. Verification of the accuracy was carried out by analysis of a standard reference material (NIST SRM 1640e "Trace elements in natural water"). The method was successfully applied to the determination of cobalt in drinking water samples.

Preconcentration and determination of tellurium in garlic samples by hydride generation atomic absorption spectrometry.

A procedure for the determination of traces of total tellurium (Te) in garlic (Allium sativa) is described that combines hydride generation atomic absorption spectrometry with preconcentration of the analyte by coprecipitation. The samples, each spiked with lanthanum nitrate (20 mg/L), are introduced into an Amberlite XAD-4 resin and mixed with ammonium buffer (pH 9.1). Te is preconcentrated by coprecipitation with the generated lanthanum hydroxide precipitate. The precipitate is quantitatively collected in the resin, eluted with hydrochloric acid, and then transferred into the atomizer device. Considering a sample consumption of 25 mL, an enrichment factor of 10 was obtained. The detection limit (3sigma) was 0.03 microg/L, and the precision (relative standard deviation) was 3.5% (n = 10) at the 10 microg/L level. The calibration graph using the preconcentration system for Te was linear with a correlation coefficient of 0.9993. Satisfactory results were obtained for the analysis of Te in garlic samples.

Cloud point preconcentration prior to capillary zone electrophoresis: simultaneous determination of platinum and palladium at trace levels.

The incorporation of a cloud point extraction (CPE) step prior to capillary electrophoresis (CE) for simultaneously determining platinum and palladium at sub-microg/L levels is presented and evaluated. The analytes were extracted as 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complexes, at pH 2.0, mediated by micelles of the nonionic surfactant polyethyleneglycolmono-p-nonylphenyl ether (PONPE 7.5). The separation-determination step was developed from 150 microL of the extracted surfactant-rich phase diluted with 50 microL of acetonitrile (ACN). An exhaustive study of the variables affecting the cloud point extraction with PONPE 7.5 and the CZE step was done. The type and composition of the background electrolytes (BGEs) were investigated with respect to separation selectivity, reproducibility, and stability. A BGE of 50 mM monobasic sodium phosphate containing 30% ACN, pH 4.53 was found to be optimal for the separation of metal chelates. Detection was performed at 576 nm. An enrichment factor of 250 was obtained for the preconcentration of 50 mL of sample solution. The detection limits for the preconcentration of 50 mL of sample were 0.04 microg/L for Pt and 0.08 microg/L for Pd. As an analytical demonstration, ultratrace concentrations of platinum and palladium were conveniently quantitated in spiked water and urine samples.

A fast method for apatite selective leaching from granitic rocks followed through rare earth elements and phosphorus determination by inductively coupled plasma optical emission spectrometry.

Rare earth elements (REE) and phosphorus (P) in apatite were determined using inductively coupled plasma optical emission spectrometry (ICP-OES) after partial dissolution of the granitic rocks and pure apatite. The dissolution was performed with nitric acid in an open system and the matrix elements were separated by a cation exchange procedure. Samples of pure apatite from granitic rocks were dissolved with, 0.14 mol L(-1) nitric acid. The results showed that the release of REE is due to apatite leaching because it could be assessed by comparing the chondrite-normalised pattern corresponding to the rocks and the pure apatite. Similar results were found for absolute REE abundance from the partial dissolution of the rocks and pure apatite. This simple and rapid method can be applied for the determination of REE in apatite as an indicator for mineral exploration, although its use in petrology could be possible.

Determination of cobalt in urine by FI-ICP-AES with online preconcentration.

A method for the preconcentration and determination of cobalt in human urine samples was developed. The online preconcentration and determination were attained using inductively coupled plasma atomic emission spectromety (ICP-AES) coupled to a flow injection (FI) method. Cobalt was retained on an Amberlite XAD-7 resin as cobalt-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol complex at pH 9.5. Cobalt was removed from the microcolumn with perchloric acid. A sensitivity enhancement factor of 90 was obtained with respect to cobalt determination by ICP-AES without preconcentration. The value of detection limit for the preconcentration method proposed was 25 ng/L. The precision for 10 replicate determinations at the 5 mg/L (mean +/- SD, 5.1 +/- 0.14) Co level was 2.7% relative standard deviation, calculated from the peak heights obtained. The calibration graph preconcentration method for cobalt was linear with a correlation coefficient of 0.9994 from approximately 0.25 mg/L up to at least 100 mg/L. The method was successfully applied to the determination of cobalt in human urine samples.