Lenys Fernández

Characterization of a carbon paste electrode modified with tripolyphosphate-modified kaolinite clay for the detection of lead

We report about the use of carbon paste electrode modified with kaolinite for analytical detection of trace lead(II) in domestic water by differential pulse voltammetry. Kaolinite clay was modified with tripolyphosphate (TPP) by impregnation method. The results show that TPP in kaolinite clay plays an important role in the accumulation process of Pb(II) on the modified electrode surface. The electroanalytical procedure for determination of Pb(II) comprised two steps: chemical accumulation of the analyte under open-circuit conditions, followed by electrochemical detection of the pre-concentrated species using differential pulse voltammetry. The analytical performance of this system has been explored by studying the effects of preconcentration time, carbon paste composition, pH, supporting electrolyte concentration, as well as interferences due to other ions. The calculated detection limit based on the variability of a blank solution (3s(b) criterion) for 10 measurements was 8.4×10(-8) mol L(-1), and the sensitivity determined from the slope of the calibration graph was 0.910 mol L(-1). The reproducibility (RSD) for five replicate measurements at 1.0 mg L(-1) lead level was 1.6%. The results indicate that this electrode is sensitive and effective for the determination of Pb(2+).

Electrochemical determination of arsenic in natural waters using carbon fiber ultra-microelectrodes modified with gold nanoparticles.

We have developed an anodic stripping voltammetry method that employs carbon fiber ultra-microelectrodes modified with gold nanoparticles to determine arsenic in natural waters. Gold nanoparticles were potentiostatically deposited on carbon fiber ultra-microelectrodes at -0.90V (vs SCE) for a time of 15s, to form the carbon fiber ultra-microelectrodes modified with gold nanoparticles. Cyclic voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy coupled to an X-ray microanalysis system were used to check and confirm the presence of gold nanoparticles on the carbon fiber ultra-microelectrodes. Arsenic detection parameters such as deposition potential and deposition time were optimized allowing a detection range between 5 to 60µgL-1. The developed modified electrodes allowed rapid As determination with improved analytical characteristics including better repeatability, higher selectivity, lower detection limit (0.9μgL-1) and higher sensitivity (0.0176nAμgL-1) as compared to the standard carbon electrodes. The analytical capability of the optimized method was demonstrated by determination of arsenic in certified reference materials (trace elements in water (NIST SRM 1643d)) and by comparison of results with those obtained by hydride generation atomic absorption spectrometry (HG-AAS) in the determination of the analyte in tap and well waters.

Electrochemical generation of antimony volatile species, stibine, using gold and silver mercury amalgamated cathodes and determination of Sb by flame atomic absorption spectrometry

The electrochemical generation of antimony volatile species (stibine) using Au and Ag mercury amalgamated cathodes is described. Compared with some other cathode materials commonly used for electrochemical hydride generation, performance of the amalgamated cathodes is substantially better in the following aspects: higher interference tolerance, higher erosion resistance and longer useful working time. Using the amalgamated cathodes, it could be shown that interferences from major constituents at high concentrations, especially from transition metals, affecting stibine generation are not as significant as they are using other cathode types in regards to sensitivity and useful working time. Results obtained using the Ag/Hg amalgamated cathode showed a slightly higher sensitivity than the corresponding results obtained using the Au/Hg cathode. The Au/Hg cathode, which to our knowledge has not previously been used to generate stibine, showed considerably longer useful working time than the Ag/Hg one. The optimum catholytes for electrolytic generation of stibine (SbH3) from Sb(III) and Sb(V) using the Au/Hg electrode were aqueous solutions containing 0.5mol L(-1) H2SO4 and 0.5mol L(-1)HCl, respectively. Under optimized conditions, using the Au/Hg cathode and comparing to aqueous standards calibration curves, detection limits (3σ) of 0.027µg L(-1) for Sb(III) and 0.056µg L(-1) for Sb(V), were obtained. To check accuracy a marine sediment reference material (PACS-2, NRC) was analyzed using a method purportedly developed for this task. Good agreement, 95% confidence, was found between the certified and the experimental values for Sb. The proposed method was also applied to the determination of Sb in aqueous solutions of marine sediments samples from Comuna de Bajo Alto Provincia de El Oro-Ecuador. Recoveries of five replicate determinations of these samples were in the range of 98-103% thus showing acceptable accuracy in the analysis of real samples.

ELECTROCHEMICAL OXIDATION OF ETHYLENE AT PANI/Pt AND Ag/PANI/Pt MODIFIED ELECTRODES

The electrochemical behavior of ethylene on PANI/Pt and Ag/PANI/Pt modified electrodes was investigated in different media. Morphology of the deposits of PANI were observed by SEM analysis, complemented by the EDX techniques to obtain the Ag composition that shows that Ag is deposited in the polymeric matrix which covered the whole platinum surface. The electrodic system comprising Ag/PANI/ Pt electrode exhibited a more important electrocatalytic response for ethylene oxidation in neutral solutions than the PAN/Pt and Pt electrodes at 20 oC.The results suggest that the oxidation of ethylene on Ag/PANI/Pt electrode is limited by adsorption-controlled reaction while the oxidation at PANI/Pt is mass transport-limited.

Improvements in the electrochemical generation of arsine at gold electrodes as a sample introduction strategy for arsenic determination in well-water samples by atomic absorption spectrometry

ABSTRACT The development and evaluation of a cathode consisting of a gold electrode covered by a polyaniline film, PANI/Au modified electrode, for electrochemical generation of arsine is described. The efficiency of arsine production using the new electrode was ascertained by comparison with corresponding hydride generation atomic absorption spectroscopy determinations of arsenic (As) in aqueous standards. The PANI/Au modified electrodes provide better sensitivity, accuracy and precision than the pure Au cathodes. The PANI/Au cathodes were prepared by controlled electrodeposition cycles of polyaniline films on top of Au electrodes. Cathodes obtained after 10 electrodeposition cycles showed the best performance, while the ones obtained after five voltammetry cycles produced films too thin and those obtained after 20 voltammetry cycles produced films too thick for the purpose of this work. Under optimised conditions, the As limit of detection in aqueous solutions, according to the (3σ) criterion, was 2.48 µg L−1. For accuracy determination, the modified electrode was applied to quantification of As(III) in acidified aqueous solutions of the certified standard reference material, NIST SRM 1643d, and in well-water samples containing possible interfering ions. Application of the Student’s t-test showed no significant difference between the expected and obtained results of the NIST SRM standard analysis at the 95% confidence level. Values for six replicate determinations of As(III) in the well-water samples showed close agreement with values obtained by analyses using hydride generation atomic absorption. Recoveries were in the range of 95–105% at test for acceptable accuracy in the analysis of real samples.

Electrochemical determination of lead in human blood serum and urine by anodic stripping voltammetry using glassy carbon electrodes covered with Ag–Hg and Ag–Bi bimetallic nanoparticles

The evaluation and application of glassy carbon electrodes modified with bimetallic nanoparticle deposits of Ag–Hg and Ag–Bi for determination of Pb(II) is described. Deposition of the nanostructured bimetallic combinations on top of the glassy carbon (GC) substrate, previously covered with a Nafion (Nf) film, resulted in electrodes with substantially enlarged hydrogen evolution over-voltage. As indicated by scanning electron microscopy and atomic force microscopy images, most of the deposited nanoparticles, with an average size of 150 nm, were uniformly dispersed inside the Nafion net while a smaller amount remained on top of the embedded ones. Sensitivity tests of the AgBiNpNf/GC modified electrode produced a detection limit (DL), based on the 3s criterion, of 0.66 μg L−1 and 0.24 μg L−1 for the AgHgNpNf/GC electrode. Accuracy was assessed by comparison with quantification of Pb(II) in human blood serum and urine samples analyzed by atomic absorption spectrometry, using a continuous source high resolution atomic absorption spectrometer.