A multiresidue method for the analysis of carbamate and urea pesticides from soils by microwave-assisted extraction and liquid chromatography with photodiode array detection

A multiresidue approach using microwave-assisted extraction and liquid chromatography with photodiode array detection was investigated for the determination of butylate, carbaryl, carbofuran, chlorpropham, ethiofencarb, linuron,metobromuron, and monolinuron in soils. The critical parameters of the developed methodology were studied. Method validation was performed by analyzing freshly and aged spiked soil samples. The recoveries and relative standard deviations reached using the optimized conditions were between 77.0 ± 0.46% and 120 ± 2.9% except for ethiofencarb (46.4 ± 4.4% to 105 ± 1.6%) and butylate (22.1 ± 7.6% to 49.2 ± 11%). Soil samples from five locations of Portugal were analysed.

Static and hydrodynamic monitoring of citalopram based on its electro-oxidation behavior at a glassy-carbon surface

The electrooxidative behavior of citalopram (CTL) in aqueous media was studied by cyclic voltammetry (CV) and square-wave voltammetry (SWV) at a glassy-carbon electrode. The electrochemical behaviour of CTL involves two electrons and two protons in the irreversible and diffusion controlled oxidation of the tertiary amine group. The maximum analytical signal was obtained in a phosphate buffer (pH ¼ 8.2). For analytical purposes, an SWV method and a flow-injection analysis (FIA) system with amperometric detection were developed. The optimised SWV method showed a linear range between 1.10 10 5–1.20 10 4 molL 1, with a limit of detection (LOD) of 9.5 10 6 molL 1. Using the FIA method, a linear range between 2.00 10 6–9.00 10 5 molL 1 and an LODof 1.9 10 6 molL 1 were obtained. The validation of both methods revealed good performance characteristics confirming applicability for the quantification of CTL in several pharmaceutical products.

Electrochemical analysis of opiates—an overview

The analysis of opiates is of vital interest in drug abuse monitoring and research. This review presents a general overview of the electrochemical methods used for detection and quantification of opiates in a variety of matrices. Emphasis has been placed on the voltammetric methods used for study and determination of morphine, codeine, and heroin. Specific issues that need to be solved and better explained as well as future trends in the use of electrochemical methods in the examination of opiates are also discussed.

Soil vapor extraction in sandy soils: influence of airflow rate

Airflow rate is one of the most important parameters for the soil vapor extraction of contaminated sites, due to its direct influence on the mass transfer occurring during the remediation process. This work reports the study of airflow rate influence on soil vapor extractions, performed in sandy soils contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene and perchloroethylene. The objectives were: (i) to analyze the influence of airflow rate on the process; (ii) to develop a methodology to predict the remediation time and the remediation efficiency; and (iii) to select the most efficient airflow rate. For dry sandy soils with negligible contents of clay and natural organic matter, containing the contaminants previously cited, it was concluded that: (i) if equilibrium between the pollutants and the different phases present in the soil matrix was reached and if slow diffusion effects did not occur, higher airflow rates exhibited the fastest remediations, (ii) it was possible to predict the remediation time and the efficiency of remediation with errors below 14%; and (iii) the most efficient remediation were reached with airflow rates below 1.2 cm3 s 1 standard temperature and pressure conditions.

Electrochemical determination of antioxidant capacities in flavored waters by guanine and adenine biosensors

The immobilization and electro-oxidation of guanine and adenine asDNA bases on glassy carbon electrode are evaluated by square wave voltammetric analysis. The influence of electrochemical pretreatments, nature of supporting electrolyte, pH, accumulation time and composition of DNA nucleotides on the immobilization effect and the electrochemical mechanism are discussed. Trace levels of either guanine or adenine can be readily detected following short accumulation time with detection limits of 35 and 40 ngmL−1 for guanine and adenine, respectively. The biosensors of guanine and adenine were employed for the voltammetric detection of antioxidant capacity in flavored water samples. The method relies on monitoring the changes of the intrinsic anodic response of the surface-confined guanine and adenine species, resulting from its interaction with free radicals from Fenton-type reaction in absence and presence of antioxidant. Ascorbic acid was used as standard to evaluate antioxidant capacities of samples. Analytical data was compared with that of FRAP method.

Square-wave voltametric method for determination of molinate concentration in a biological process using a hanging mercury drop electrode

A square-wave voltammetric (SWV) method using a hanging mercury drop electrode (HMDE) has been developed for determination of the herbicide molinate in a biodegradation process. The method is based on controlled adsorptive accumulation of molinate for 10 s at a potential of -0.8 V versus AgCl/Ag. An anodic peak, due to oxidation of the adsorbed pesticide, was observed in the cyclic voltammogram at ca. -0.320 V versus AgCl/Ag; a very small cathodic peak was also detected. The SWV calibration plot was established to be linear in the range 5.0x10-6 to 9.0x10-6 mol L-1; this corresponded to a detection limit of 3.5x10-8 mol L-1. This electroanalytical method was used to monitor the decrease of molinate concentration in river waters along a biodegradation process using a bacterial mixed culture. The results achieved with this voltammetric method were compared with those obtained by use of a chromatographic method (HPLC–UV) and no significant statistical differences were observed.

Oxidative behaviour of apomorphine and its metabolites

The metabolism of apomorphine is quite complex due to interactions with proteins and other tissue components that affect its pharmacokinetic profile. The electrochemical oxidation mechanism of apomorphine and of some synthesised apomorphine derivatives was studied. It was found to be related to the reaction of o-diphenol and tertiary amine groups and strongly dependent on pH.

Development of electrochemical methods for determination of tramadol - analytical application to pharmaceutical dosage forms

A square-wave voltammetric (SWV) method and a flow injection analysis system with amperometric detection were developed for the determination of tramadol hydrochloride. The SWV method enables the determination of tramadol over the concentration range of 15-75 µM with a detection limit of 2.2 µM. Tramadol could be determined in concentrations between 9 and 50 µM at a sampling rate of 90 h-1, with a detection limit of 1.7 µM using the flow injection system. The electrochemical methods developed were successfully applied to the determination of tramadol in pharmaceutical dosage forms, without any pre-treatment of the samples. Recovery trials were performed to assess the accuracy of the results; the values were between 97 and 102% for both methods.

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.

Determination of free furfuryl alcohol in foundry resins by chromatographic techniques

Two chromatographic methods, gas chromatography with flow ionization detection (GC–FID) and liquid chromatography with ultraviolet detection (LC–UV), were used to determine furfuryl alcohol in several kinds of foundry resins, after application of an optimised extraction procedure. The GC method developed gave feasibility that did not depend on resin kind. Analysis by LC was suitable just for furanic resins. The presence of interference in the phenolic resins did not allow an appropriate quantification by LC. Both methods gave accurate and precise results. Recoveries were >94%; relative standard deviations were ≤7 and ≤0.3%, respectively for GC and LC methods. Good relative deviations between the two methods were found (≤3%).

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.

Electrochemical oxidation of propanil and related N-substituted amides

The electrochemical behaviour of propanil and related N-substituted amides (acetanilide and N,N-diphenylacetamide) was studied by cyclic and square wave voltammetry using a glassy carbon electrode. Propanil has been found to have chemical stability under the established analytical conditions and showed an oxidation peak at +1.27V versus Ag/AgCl at pH 7.5. N,N-diphenylacetamide has a higher oxidation potential than the other compounds of +1.49V versus Ag/AgCl. Acetanilide oxidation occurred at a potential similar to that of propanil, +1.24V versus Ag/AgCl. These results are in agreement with the substitution pattern of the nitrogen atom of the amide. A degradation product of propanil, 3,4-dichloroaniline (DCA), was also studied, and showed an oxidation peak at +0.66V versus Ag/AgCl. A simple and specific quantitative electroanalytical method is described for the analysis of propanil in commercial products that contain propanil as the active ingredient, used in the treatment of rice crops in Portugal.

Electroanalytical determination of codeine in pharmaceutical preparations

A square wave voltammetric (SWV) method and a flow injection analysis systemwi th electrochemical detection (FIA-EC) using a glassy carbon electrode were evaluated for the determination of codeine in pharmaceutical preparations. The interference of several compounds, such as acetaminophen,guaiacol, parabens, ephedrine, acetylsalicylic acid and caffeine, that usually appear associated with codeine pharmaceutical preparations was studied. It was verified that these electroanalytical methods could not be used with acetaminophen present in the formulations and that with guaiacol, parabens or ephedrine present the use of the FIA-EC system was impracticable. A detection limit of 5 µmol L- 1 and a linear calibration range from 40 to 140 µmol L- 1 was obtained with the SWV method. For the flow injection analysis procedure a linear calibration range was obtained from 7 to 50 µmol L- 1 with a detection limit of 3 µmol L- 1 and the FIA-EC systemallowed a sampling rate of 115 samples per hour. The results obtained by the two methods, SWV and FIA-EC, were compared with those obtained using reference methods and demonstrated good agreement, with relative deviations lower than 4%.

Determination of carbamate and urea pesticide residues in fresh vegetables using microwave-assisted extraction and liquid chromatography

An analytical multiresidue method for the simultaneous determination of seven pesticides in fresh vegetable samples, namely, courgette (Cucurbita pepo), cucumber (Cucumis sativus), lettuce (Lactuca sativa, Romaine and Iceberg varieties) and peppers (Capsicum sp.) is described. The procedure, based on microwave-assisted extraction (MAE) and analysis by liquid chromatography– photodiode array (LC–PDA) detection was applied to four carbamates (carbofuran, carbaryl, chlorpropham and EPTC) and three urea pesticides (monolinuron, metobromuron and linuron). Extraction solvent and the addition of anhydrous sodium sulphate to fresh vegetable homogenate before MAE were the parameters optimised for each commodity. Recovery studies were performed using spiked samples in the range 250–403 µgkg- 1 in each pesticide. The pesticide residues were extracted using 20mL acetonitrile at 60 ºC, for 10 min. Acceptable recoveries and RSDs were attained (overall average recovery of 77.2% and RSDs are lower than 11%). Detection limits ranged between 5.8 µgkg- 1 for carbaryl to 12.3 µgkg- 1 for carbofuran. The analytical protocol was applied for quality control of 41 fresh vegetable samples bought in Oporto Metropolitan Area (North Portugal). None of the samples contained any detectable amounts of the studied compounds.