Highly Sensitive Electrochemical Sensor for Determination of Vitamin D in Mixtures of Water-Ethanol

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Determination of furanic aldehydes in sugarcane bagasse by high-performance liquid chromatography with pulsed amperometric detection using a modified electrode with nickel nanoparticles

A glassy carbon electrode chemically modified with nickel nanoparticles coupled with reversed-phase chromatography with pulsed amperometric detection was used for the quantitative analysis of furanic aldehydes in a real sample of sugarcane bagasse hydrolysate. Chromatographic separation was carried out in isocratic conditions (acetonitrile/water, 1:9) with a flow rate of 1.0 mL/min, a detection potential of -50 mV vs. Pd, and the process was completed within 4 min. The analytical curves presented limits of detection of 4.0 × 10(-7) mol/L and 4.3 × 10(-7) mol/L, limits of quantification of 1.3 × 10(-6) and 1.4 × 10(-6) mol/L, amperometric sensitivities of 2.2 × 10(6) nA mol/L and 2.7 × 10(6) nA mol/L for furfural and 5-hydroxymethylfurfural, respectively. The values obtained in this sample by the standard addition method were 1.54 ± 0.02 g/kg for 5-hydroxymethylfurfural and 11.5 ± 0.2 g/kg for furfural. The results demonstrate that this new proposed method can be used for the quick detection of furanic aldehydes without the interference of other electroactive species, besides having other remarkable merits that include excellent peak resolution, analytical repeatability, sensitivity, and accuracy.

Preparation of a clay-modified carbon paste electrode based on 2-thiazoline-2-thiol-hexadecylammonium sorption for the sensitive determination of mercury

A montmorillonite from Wyoming-USA was used to prepare an organo-clay complex, named 2-thiazoline-2-thiol-hexadecyltrimethylammonium-clay (TZT-HDTA-clay), for the purpose of the selective adsorption of the heavy metals ions and possible use as a chemically modified carbon paste electrode (CMCPE). Adsorption isotherms of Hg 2+, Pb 2+, Cd 2+, Cu 2+, and Zn 2+ from aqueous solutions as a function of the pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The organo-clay complex was very selective to Hg(II) in aqueous solution in which other metals and ions were also present. The accumulation voltammetry of Hg(II) was studied at a carbon paste electrode chemically modified with this material. The mercury response was evaluated with respect to the pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. A carbon paste electrode modified by TZT-HDTA-clay showed two peaks: one cathodic peak at about 0.0 V and an anodic peak at 0.25 V, scanning the potential from -0.2 to 0.8 V (0.05 M KNO 3 vs. Ag/AgCl). The anodic peak at 0.25 V presents excellent selectivity for Hg(II) ions in the presence of foreign ions. The detection limit was estimated as 0.1 μg L -1. The precision of determination was satisfactory for the respective concentration level. 2005 © The Japan Society for Analytical Chemistry.

Use of Gas Diffusion Electrode for the In Situ Generation of Hydrogen Peroxide in an Electrochemical Flow-By Reactor

Hydrogen peroxide is a powerful oxidant that finds application in several areas, but most particularly in the treatment of industrial wastewaters. The aim of the present study was to investigate the effects of applied potential and electrolyte flow conditions on the in situ generation of hydrogen peroxide in an electrochemical flow-by reactor with a gas diffusion electrode (GDE). The electrolyses were performed in an aqueous acidic medium using a GDE constructed with conductive black graphite and polytetrafluoroethylene (80:20 w/w). Under laminar flow conditions (flow rate = 50 L/h), hydrogen peroxide was formed in a maximum yield of 414 mg/L after 2 h at -2.25 V vs Pt //Ag/AgCl (global rate constant = 3.1 mg/(L min); energy consumption = 22.1 kWh/kg). Under turbulent flow (300 L/h), the maximum yield obtained was 294 mg/L after 2 h at -1.75 V vs Pt//Ag/AgCl (global rate constant = 2.5 mg/ (L min); energy consumption = 30.1 kWh/kg).

A comparative study of the electrochemical oxidation of the herbicide tebuthiuron using boron-doped diamond electrode

The thiadiazolylurea derivative tebuthiuron (TBH) is commonly used as an herbicide even though it is highly toxic to humans. While various processes have been proposed for the removal of organic contaminants of this type from wastewater, electrochemical degradation has shown particular promise. The aim of the present study was to investigate the electrochemical degradation of TBH using anodes comprising boron-doped (5000 and 30000 ppm) diamond (BDD) films deposited onto Ti substrates operated at current densities in the range 10-200 mA cm(-2). Both anodes removed TBH following a similar pseudo first-order reaction kinetics with k(ap)p close to 3.2 x 10(-2) min(-1). The maximum mineralization efficiency obtained was 80%. High-pressure liquid chromatography with UV-VIS detection established that both anodes degraded TBH via similar intermediates. Ion chromatography revealed that increasing concentrations of nitrate ions (up to 0.9 ppm) were formed with increasing current density, while the formation of nitrite ions was observed with both anodes at current densities >= 150 mA cm(-2). The BDD film prepared at the lower doping level (5000 ppm) was more efficient in degrading TBH than its more highly doped counterpart. This unexpected finding may be explained in terms of the quantity of impurities incorporated into the diamond lattice during chemical vapor deposition. (C) 2012 Elsevier Ltd. All rights reserved.

Flow injection analysis of free glycerol in biodiesel using a copper electrode as an amperometric detector

The main goal of this work was to develop a simple analytical method for quantification of glycerol based on the electrocatalytic oxidation of glycerol on the copper surface adapted in a flow injection system. Under optimal experimental conditions, the peak current response increases linearly with glycerol concentration over the range 60-3200 mg kg(-1) (equivalent to 3-160 mg L(-1) in solution). The repeatability of the electrode response in the flow injection analysis (FIA) configuration was evaluated as 5% (n = 10), and the detection limit of the method was estimated to be 5 mg kg(-1) in biodiesel (equivalent to 250 mu g L(-1) in solution) (S/N = 3). The sample throughput under optimised conditions was estimated to be 90 h(-1). Different types of biodiesel samples (B100), as in the types of vegetable oils or animal fats used to produce the fuels, were analysed (seven samples). The only sample pre-treatment used was an extraction of glycerol from the biodiesel sample containing a ratio of 5 mL of water to 250 mg of biodiesel. The proposed method improves the analytical parameters obtained by other electroanalytical methods for quantification of glycerol in biodiesel samples, and its accuracy was evaluated using a spike-and-recovery assay, where all the biodiesel samples used obtained admissible values according to the Association of Official Analytical Chemists. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.

Seven years of external control of fluoride levels in the public water supply in Bauru, São Paulo, Brazil

Fluoridation of the public water supplies is recognized as among the top ten public health achievements of the twentieth century. However, the positive aspects of this measure depend on the maintenance of fluoride concentrations within adequate levels. To report the results of seven years of external control of the fluoride (F) concentrations in the public water supply in Bauru, SP, Brazil in an attempt to verify, on the basis of risk/benefit balance, whether the levels are appropriate. From March 2004 to February 2011, 60 samples were collected every month from the 19 supply sectors of the city, totaling 4,641 samples. F concentrations in water samples were determined in duplicate, using an ion-specific electrode (Orion 9609) coupled to a potentiometer after buffering with TISAB II. After the analysis, the samples were classified according to the best risk-benefit adjustment. Means (±standard deviation) of F concentrations ranged between 0.73±0.06 and 0.81±0.10 mg/L for the different sectors during the seven years. The individual values ranged between 0.03 and 2.63 mg/L. The percentages of the samples considered “low risk” for dental fluorosis development and of “maximum benefit” for dental caries prevention (0.55-0.84 mg F/L) in the first, second, third, fourth, fifth, sixth, and seventh years of the study were 82.0, 58.5, 37.4, 61.0, 89.9, 77.3, and 72.4%, respectively, and 69.0% for the entire period. Fluctuations of F levels were found in the public water supply in Bauru during the seven years of evaluation. These results suggest that external monitoring of water fluoridation by an independent assessor should be implemented in cities where there is adjusted fluoridation. This measure should be continued in order to verify that fluoride levels are suitable and, if not, to provide support for the appropriate adjustments

Isotopic composition of water in fog, rain, throughfall and stemflow in the Monte Verde, Costa Rica

Fog deposition, precipitation, throughfall and stemflow were measured in a windward tropical montane cloud forest near Monteverde, Costa Rica, for a 65-day period during the dry season of 2003. Net fog deposition was measured directly using the eddy covariance (EC) method and it amounted to 1.2 ± 0.1 mm/day (mean ± standard error). Fog water deposition was 5-9% of incident rainfall for the entire period, which is at the low end of previously reported values. Stable isotope concentrations (d18O and d2H) were determined in a large number of samples of each water component. Mass balance-based estimates of fog deposition were 1.0 ± 0.3 and 5.0 ± 2.7 mm/day (mean ± SE) when d18O and d2H were used as tracer, respectively. Comparisons between direct fog deposition measurements and the results of the mass balance model using d18O as a tracer indicated that the latter might be a good tool to estimate fog deposition in the absence of direct measurement under many (but not all) conditions. At 506 mm, measured water inputs over the 65 days (fog plus rain) fell short by 46 mm compared to the canopy output of 552 mm (throughfall, stemflow and interception evaporation). This discrepancy is attributed to the underestimation of rainfall during conditions of high wind.

Pore-water chemistry at DSDP Leg 70 Holes

Geological and geophysical data collected during Deep Sea Drilling Project (DSDP) Leg 70 indicate that hydrothermal solutions are upwelling through the sediments of the mounds hydrothermal field (Sites 506, 507, and 509) and downwelling in the low heat-flow zone to the south (Site 508). Pore-water data are compatible with these conclusions. Pore waters at mounds sites are enriched in Ca and depleted in Mg relative to both seawater and Site 508 pore waters. These anomalies are believed to reflect prior reaction of the interstitial waters with basement rocks. The mounds solutions are also enriched in iron, which is probably hydrothermal and en route to forming nontronite. Concentrations of Si and NH3 in mounds pore water increase upcore as a result of the addition of dissolving biogenic debris to ascending hydrothermal solutions. Some low heat-flow pore-water samples (Site 508) are enriched in Ca and depleted in Mg. These anomalies likely reflect the presence of pockets of hydrothermal solutions in areas otherwise dominated by downwelling bottom water.