Adsorptive stripping voltammetric determination of venlafaxine in urine with a mercury film microelectrode

An adsorptive stripping voltammetric procedure for the determination of the antidepressant venlafaxine in urine using a mercury film microelectrode wasdeveloped. The method is based on controlled adsorptive accumulation of the drug at the potential of 1.00V (vs. Ag/AgCl) in the presence of 1.25 x10 -2 molL- 1 borate buffer (pH 8.7). Urine samples were analyzed directly after performing a ten-fold dilution with the supporting electrolyte but without other pretreatment. The limit of detection obtained for a 30 s collection time was 0.693x 10- 6 mol L -1. Recovery experimentsgave good results at the 10 -6 mol L- 1 level (bias less 5% were obtained).

The development and optimization of a modified single-drop microextraction method for organochlorine pesticides determination by gas chromatography-tandem mass spectrometry

We have developed a new method for single-drop microextraction (SDME) for the preconcentration of organochlorine pesticides (OCP) from complex matrices. It is based on the use of a silicone ring at the tip of the syringe. A 5 μL drop of n-hexane is applied to an aqueous extract containing the OCP and found to be adequate to preconcentrate the OCPs prior to analysis by GC in combination with tandem mass spectrometry. Fourteen OCP were determined using this technique in combination with programmable temperature vaporization. It is shown to have many advantages over traditional split/splitless injection. The effects of kind of organic solvent, exposure time, agitation and organic drop volume were optimized. Relative recoveries range from 59 to 117 %, with repeatabilities of <15 % (coefficient of variation) were achieved. The limits of detection range from 0.002 to 0.150 μg kg−1. The method was applied to the preconcentration of OCPs in fresh strawberry, strawberry jam, and soil.

Development of polyaniline microarray electrodes for cadmium analysis

Disposable screen-printed electrodes (SPCE) were modified using a cosmetic product to partially block the electrode surface in order to obtain a microelectrode array. The microarrays formed were electropolymerized with aniline. Scanning electron microscopy was used to evaluate the modified and polymerized electrode surface. Electrochemical characteristics of the constructed sensor for cadmium analysis were evaluated by cyclic and square-wave voltammetry. Optimized stripping procedure in which the preconcentration of cadmium was achieved by depositing at –1.20 V (vs. Ag/AgCl) resulted in a well defined anodic peak at approximately –0.7 V at pH 4.6. The achieved limit of detection was 4 × 10−9 mol dm−3. Spray modified and polymerized microarray electrodes were successfully applied to quantify cadmium in fish sample digests.

Electrochemical study of butylate: application to the analysis of water

The electroactivity of butylate (BTL) is studied by cyclic voltammetry (CV) and square wave voltammetry (SWV) at a glassy carbon electrode (GCE) and a hanging mercury drop electrode (HMDE). Britton–Robinson buffer solutions of pH 1.9–11.5 are used as supporting electrolyte. CV voltammograms using GCE show a single anodic peak regarding the oxidation of BTL at +1.7V versus AgCl/ Ag, an irreversible process controlled by diffusion. Using a HMDE, a single cathodic peak is observed, at 1.0V versus AgCl/Ag. The reduction of BTL is irreversible and controlled by adsorption. Mechanism proposals are presented for these redox transformations. Optimisation is carried out univaryingly. Linearity ranges were 0.10–0.50 mmol L-1 and 2.0–9.0 µmolL-1 for anodic and cathodic peaks, respectively. The proposed method is applied to the determination of BTL in waters. Analytical results compare well with those obtained by an HPLC method.

Direct electroanalytical determination of fluvastatin in a pharmaceutical dosage form: batch and flow analysis

The reduction of luvastatin (FLV) at a hanging mercury-drop electrode (HMDE) was studied by square-wave adsorptive-stripping voltammetry (SWAdSV). FLV can be accumulated and reduced at the electrode, with a maximum peak current intensity at a potential of approximately 1.26V vs. AgCl=Ag, in an aqueous electrolyte solution of pH 5.25. The method shows linearity between peak current intensity and FLV concentration between 1.0 10 8 and 2.7 10 6 mol L 1. Limits of detection (LOD) and quantification (LOQ) were found to be 9.9 10 9 mol L 1 and 3.3 10 8 mol L 1, respectively. Furthermore, FLV oxidation at a glassy carbon electrode surface was used for its hydrodynamic monitoring by amperometric detection in a flow-injection system. The amperometric signal was linear with FLV concentration over the range 1.0 10 6 to 1.0 10 5 mol L 1, with an LOD of 2.4 10 7 mol L 1 and an LOQ of 8.0 10 7 mol L 1. A sample rate of 50 injections per hour was achieved. Both methods were validated and showed to be precise and accurate, being satisfactorily applied to the determination of FLV in a commercial pharmaceutical.

Determination of chlorfenvinphos in soils by microwave-assisted extraction and stripping voltammetry with an ultramicroelectrode

A methodology for the determination of the pesticide chlorfenvinphos by microwave-assisted solvent extraction and square-wave cathodic stripping voltammetry at a mercury film ultramicroelectrode in soil samples is proposed. Optimization of microwave solvent extraction performed with two soils, selected for having significantly different properties, indicated that the optimum solvent for extracting chlorfenvinphos is hexane-acetone (1:1, v/v). The voltammetric procedure is based on controlled adsorptive accumulation of the insecticide at the potential of -0.60 V (vs. Ag/AgCl) in the presence of Britton-Robinson buffer (pH 6.2). The detection limit obtained for a 10 s collection time was 3.0 x 10-8 mol l-1. The validity of the developed methodology was assessed by recovery experiments at the 0.100 µg g-1 level. The average recoveries and standard deviations for the global procedure reached byMASE-square-wave voltammetry were 90.2±2.8% and 92.1±3.4% for type I (soil rich in organic matter) and type II (sandy soil) samples, respectively. These results are in accordance to the expected values which show that the method has a good accuracy.

Dual augmentation for aerobic bioremediation of MTBE and TCE pollution in heavy metal-contaminated soil

In this work we isolated from soil and characterized several bacterial strains capable of either resisting high concentrations of heavy metals (Cd2+ or Hg2+ or Pb2+) or degrading the common soil and groundwater pollutants MTBE (methyl-tertbutyl ether) or TCE (trichloroethylene). We then used soil microcosms exposed to MTBE (50 mg/l) or TCE (50 mg/l) in the presence of one heavy metal (Cd 10 ppm or Hg 5 ppm or Pb 50 or 100 ppm) and two bacterial isolates at a time, a degrader plus a metalresistant strain. Some of these two-membered consortia showed degradation efficiencies well higher (49–182% higher) than those expected under the conditions employed, demonstrating the occurrence of a synergetic relationship between the strains used. Our results show the efficacy of the dual augmentation strategy for MTBE and TCE bioremediation in the presence of heavy metals.

Ecotoxicity tests using the green algae chlorella vulgaris — a useful tool in hazardous effluents management

The treatment efficiency of laboratory wastewaters was evaluated and ecotoxicity tests with Chlorella vulgaris were performed on them to assess the safety of their environmental discharge. For chemical oxygen demand wastewaters, chromium (VI), mercury (II) and silver were efficiently removedby chemical treatments.Areduction of ecotoxicitywas achieved; nevertheless, an EC50 (effective concentration that causes a 50% inhibition in the algae growth) of 1.5% (v/v) indicated still high level of ecotoxicity. For chloride determination wastewaters, an efficient reduction of chromium and silver was achieved after treatment. Regarding the reduction of ecotoxicity observed, EC50 increased from 0.059% to 0.5%, only a 0.02% concentration in the aquatic environment would guarantee no effects. Wastewaters containing phenanthroline/iron (II) complex were treated by chemical oxidation. Treatmentwas satisfactory concerning chemical parameters, although an increase in ecotoxicitywas observed (EC50 reduced from 0.31% to 0.21%). The wastes from the kinetic study of persulphate and iodide reaction were treated with sodium bisulphite until colour was removed. Although they did not reveal significant ecotoxicity, only over 1% of the untreated waste produced observable effects over algae. Therefore, ecotoxicity tests could be considered a useful tool not only in laboratory effluents treatment, as shown, but also in hazardous wastewaters management.

Electrochemical determination of citalopram by adsorptive stripping voltammetry–determination in pharmaceutical products

The electrochemical behavior of citalopram was studied by square-wave and square-wave adsorptive-stripping voltammetry (SWAdSV). Citalopram can be reduced and accumulated at a mercury drop electrode, with a maximum peak current intensity being obtained at a potential of approximately -1.25V vs. AgCl/Ag, in an aqueous electrolyte solution of pH 12. A SWAdSV method has been developed for the determination of citalopram in pharmaceutical preparations. The method shows a linear range between 1.0x10-7 and 2.0x10-6 mol L-1 with a limit of detection of 5x10-8 mol L-1 for an accumulation time of 30 s. The precision of the method was evaluated by assessing the repeatability and intermediate precision, achieving good relative standard deviations in all cases (≤2.3%). The proposed method was applied to the determination of citalopram in five pharmaceutical products and the results obtained are in good agreement with the labeled values.

Electroanalytical study of fluvoxamine

Fluvoxamine (FVX) can be reduced at a mercury- drop electrode, with a maximum peak current intensity being obtained at a potential of -0.7 V vs. Ag/ AgCl, in an aqueous electrolyte solution of pH 2. The compound was determined in a pharmaceutical product and in spiked human serum by square-wave adsorptivestripping voltammetry (SWAdSV) after accumulation at the electrode surface, under batch conditions. Because the presence of dissolved oxygen did not interfere significantly with the analysis, it was also possible to determine FVX in the pharmaceutical product by use of a flow-injection analysis (FIA) system with SWAdSV detection. The methods developed were validated and successfully applied to the quantification of FVX in a pharmaceutical product. Recoveries between 76 and 89% were obtained in serum analysis. The FIA– SWAdSV method enabled analysis of up to 120 samples per hour at reduced cost, implying the possibility of competing with the chromatographic methods usually used for this analysis.

Electroanalytical determination of paroxetine in pharmaceuticals

Electroanalytical methods based on square-wave adsorptive-stripping voltammetry (SWAdSV) and flow-injection analysis with SWAdSV detection (FIA-SWAdSV) were developed for the determination of paroxetine (PRX). The methods were based on the reduction of PRX at a mercury drop electrode at −1.55V versus Ag/AgCl, in a borate buffer of pH 8.8, and the possibility of accumulating the compound at the electrode surface. Because the presence of dissolved oxygen did not interfere significantly with the analysis, it was also possible to determine PRX using FIASWAdSV. This method enables analysis of up to 120 samples per hour at reduced costs. Both methods developed were validated and successfully applied to the quantification of PRX in pharmaceutical products.

Adsorption behavior of α-cypermethrin on cork and activated carbon

Studies were undertaken to determine the adsorption behavior of α-cypermethrin [R)-α-cyano-3-phenoxybenzyl(1S)-cis- 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, and (S)-α-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dichlorovinyl)-2,2- dimethylcyclopropanecarboxylate] in solutions on granules of cork and activated carbon (GAC). The adsorption studies were carried out using a batch equilibrium technique. A gas chromatograph with an electron capture detector (GC-ECD) was used to analyze α-cypermethrin after solid phase extraction with C18 disks. Physical properties including real density, pore volume, surface area and pore diameter of cork were evaluated by mercury porosimetry. Characterization of cork particles showed variations thereby indicating the highly heterogeneous structure of the material. The average surface area of cork particles was lower than that of GAC. Kinetics adsorption studies allowed the determination of the equilibrium time—24 hours for both cork (1–2 mm and 3–4 mm) and GAC. For the studied α-cypermethrin concentration range, GAC revealed to be a better sorbent. However, adsorption parameters for equilibrium concentrations, obtained through the Langmuir and Freundlich models, showed that granulated cork 1–2 mm have the maximum amount of adsorbed α-cypermethrin (qm) (303 μg/g); followed by GAC (186 μg/g) and cork 3-4 mm (136 μg/g). The standard deviation (SD) values, demonstrate that Freundlich model better describes the α-cypermethrin adsorption phenomena on GAC, while α-cypermethrin adsorption on cork (1-2 mm and 3-4 mm) is better described by the Langmuir. In view of the adsorption results obtained in this study it appears that granulated cork may be a better and a cheaper alternative to GAC for removing α-cypermethrin from water.

Electroanalytical study of the antidepressant sertraline

Aflowinjection squarewave cathodic stripping voltammetric method has been developed for the determination of sertraline in a pharmaceutical preparation. The method shows linearity between peak current intensity and sertraline concentration for the interval between 0.20×10−6 and 1.20×10−6 mol L−1. Limits of detection and quantification were found to be 1.5×10−7 and 5.0×10−7 mol L−1, respectively. Up to 70 samples per hour can be analysed with a good precision (R.S.D. = 2.5%). The proposed method was successfully applied to the determination of sertraline in a commercial product. In the voltammetric determination of sertraline in flow, a high sample rate is obtained at reduced costs, opening the possibility to compete with the chromatographic methods generally used for this analysis.

Electroanalytical study of the pesticide ethiofencarb

A detailed study of voltammetric behavior of ethiofencarb (ETF) is reported using glassy carbon electrode (GCE) and hanging mercury drop electrode (HMDE). With GCE, it is possible to verify that the oxidative mechanism is irreversible, independent of pH, and the maximum intensity current was observed at +1.20 V vs. AgCl/Ag at pH 1.9. A linear calibration line was obtained from 1.0x10-4 to 8.0x10-4 mol L-1 with SWV method. To complete the electrochemical knowledge of ETF pesticide, the reduction was also explored with HMDE. A well-defined peak was observed at –1.00V vs. AgCl/Ag in a large range of pH with higher signal at pH 7.0. Linearity was obtained in 4.2x10-6 and 9.4x10-6 mol L-1 ETF concentration range. An immediate alkaline hydrolysis of ETF was executed, producing a phenolic compound (2-ethylthiomethylphenol) (EMP), and the electrochemical activity of the product was examined. It was deduced that it is oxidized on GCE at +0.75V vs. AgCl/Ag with a maximum peak intensity current at pH 3.2, but the compound had no reduction activity on HMDE. Using the decrease of potential peak, a flow injection analysis (FIA) system was developed connected to an amperometric detector, enabling the determination of EMP over concentration range of 1.0x10-7 and 1.0x10-5 mol L-1 at a sampling rate of 60 h-1. The results provided by FIA methodology were performed by comparison with results from high-performance liquid chromatography (HPLC) technique and demonstrated good agreement with relative deviations lower than 4%. Recovery trials were performed and the obtained values were between 98 and 104%.

Multiple linear and principal component regressions for modelling ecotoxicity bioassay response

The ecotoxicological response of the living organisms in an aquatic system depends on the physical, chemical and bacteriological variables, as well as the interactions between them. An important challenge to scientists is to understand the interaction and behaviour of factors involved in a multidimensional process such as the ecotoxicological response.With this aim, multiple linear regression (MLR) and principal component regression were applied to the ecotoxicity bioassay response of Chlorella vulgaris and Vibrio fischeri in water collected at seven sites of Leça river during five monitoring campaigns (February, May, June, August and September of 2006). The river water characterization included the analysis of 22 physicochemical and 3 microbiological parameters. The model that best fitted the data was MLR, which shows: (i) a negative correlation with dissolved organic carbon, zinc and manganese, and a positive one with turbidity and arsenic, regarding C. vulgaris toxic response; (ii) a negative correlation with conductivity and turbidity and a positive one with phosphorus, hardness, iron, mercury, arsenic and faecal coliforms, concerning V. fischeri toxic response. This integrated assessment may allow the evaluation of the effect of future pollution abatement measures over the water quality of Leça River.