Evaluation of a gold-nanoparticle-modified carbon-fiber microelectrode to quantify mercury in canned tuna sold in Ecuador.

Seafood consumption is the primary exposure route for trace metals like mercury. Accordingly, canned tuna meat has been focused on by researchers because of the potential bioaccumulation of high amounts of mercury. This study aimed to test a novel and reliable electroanalytical method employing a working electrode consisting of gold-nanoparticle-modified carbon microfibers to quantify total mercury in canned tuna samples. Determination was achieved via differential pulse anodic stripping voltammetry. The proposed method had a limit of detection of 3.9781 ± 0.0001 µg L-1 and a limit of quantification of 33.6634 ± 0.0001 µg L-1, with a sensitivity of 0.3275 nA µg L-1. The modified electrode was evaluated in samples taken from three canned tuna brands sold in the Sangolquí parish in Rumiñahui, Ecuador. These brands, coded A, B, and C, represent 47.92%, 27.08%, and 11.98% of all canned tuna sold in the Ecuadorian market, respectively. The resulting respective total mercury concentrations were 0.5999 ± 0.0001 mg kg-1; 0.9387 ± 0.0001 mg kg-1; and 0.3442 ± 0.0001 mg kg-1 for A, B, and C. Method accuracy was determined through the recovery percentages of ≥98%, which indicated acceptable accuracy for the final optimized method. Mean mercury concentrations for all samples did not represent a carcinogenic risk for consumers. However, the values obtained for potential no-carcinogenic risk and daily consumption rate suggest that consumers of tuna canned in water, particularly brand C, may be at risk.

Photoelectrocatalytic degradation of diclofenac with a boron-doped diamond electrode modified with titanium dioxide as a photoanode.

The electrophoretic deposition of titanium dioxide (TiO2) nanoparticles (Degussa P25) onto a boron-doped diamond (BDD) substrate was carried out to produce a photoanode (TiO2/BDD) to apply in the degradation and mineralization of sodium diclofenac (DCF-Na) in an aqueous medium using photoelectrocatalysis (PEC). This study was divided into three stages: i) photoanode production through electrophoretic deposition using three suspensions (1.25%, 2.5%, 5.0% w/v) of TiO2 nanoparticles, applying 4.8 V for 15 and 20 s; ii) characterization of the TiO2/BDD photoanode using scanning electron microscopy and cyclic voltammetry response with the [Fe(CN)6]3-/4- redox system; iii) degradation of DCF-Na (25 mg L-1) through electrochemical oxidation (EO) on BDD and PEC on TiO2/BDD under dark and UVC-light conditions. The degradation of DCF-Na was evaluated using high-performance liquid chromatography and UV-Vis spectroscopy, and its mineralization measured using total organic carbon and chemical oxygen demand. The results showed that after 2 h, DCF-Na degradation and mineralization reached 98.5% and 80.1%, respectively, through PEC on the TiO2/BDD photoanode at 2.2 mA cm-2 under UVC illumination, while through EO on BDD applying 4.4 mA cm-2, degradation and mineralization reached 85.6% and 76.1%, respectively. This difference occurred because of the optimal electrophoretic formation of a TiO2 film with a 9.17 µm thickness on the BDD (2.5% w/v TiO2, time 15 s, 4.8 V), which improved the electrocatalysis and oxidative capacity of the TiO2/BDD photoanode. Additionally, PEC showed a lower specific energy consumption (1.55 kWh m-3). Thus, the use of nanostructured TiO2 films deposited on BDD is an innovative photoanode alternative for the photoelectrocatalytic degradation of DCF-Na, which substantially improves the degradation capacity of bare BDD.

Development and Evaluation of Copper Electrodes, Modified with Bimetallic Nanoparticles, to be Used as Sensors of Cysteine-Rich Peptides Synthesized by Tobacco Cells Exposed to Cytotoxic Levels of Cadmium.

We report on two new electrochemical sensors which, coupled to differential pulse voltammetry, constitutes a useful tool for diagnosis of heavy metal pollution. The electrochemical sensors AgHgNf/Cu and the AgBiNf/Cu were obtained by deposition of bimetallic particles of AgHg or AgBi on copper electrodes covered with a Nafion (Nf) film, respectively. Micrographs of the electrode's surface showed evenly scattered bimetallic particles, with an approximate diameter of 150 nm, embedded in the Nafion (Nf) film. In order to test the electrodes, the hydrogen evolution signal according to the Brdicka reaction was measured for the determination of cysteine-rich peptides (CRp) produced by plants. To check the accuracy of the electrodes, real samples of Nicotiana tabacum cells exposed to cytotoxic levels of cadmium were tested. The AgHgNf/Cu electrode produced detection limits (DLs) of 0.088 µmol L-1 for Cysteine and 0.139µmol L-1 for Glutathione, while for the AgBiNf/Cu electrode DLs were 0.41 µmol L-1 for cysteine and 0.244 µmol L-1 for glutathione. Thus, the new electrodes could be a useful analytical electrochemical system very convenient for fieldwork. The electrodes were capable of direct, accurate, and sensitive detection of synthesized peptides, despite the complex matrix where the Nicotiana tabacum cells were grown.

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.