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Phenol is a toxic compound present in a wide variety of foundry resins. Its quantification is important for the characterization of the resins as well as for the evaluation of free contaminants present in foundry wastes. Two chromatographic methods, liquid chromatography with ultraviolet detection (LC-UV) and gas chromatography with flame ionization detection (GC-FID), for the analysis of free phenol in several foundry resins, after a simple extraction procedure (30 min), were developed. Both chromatographic methods were suitable for the determination of phenol in the studied furanic and phenolic resins, showing good selectivity, accuracy (recovery 99-100%; relative deviations <5%), and precision (coefficients of variation <6%). The used ASTM reference method was only found to be useful in the analysis of phenolic resins, while the LC and GC methods were applicable for all the studied resins. The developed methods reduce the time of analysis from 3.5 hours to about 30 min and can readily be used in routine quality control laboratories. [ABSTRACT FROM AUTHOR]

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 = 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 mol L-1, with a limit of detection (LOD) of 9.5 × 10-6 mol L-1. Using the FIA method, a linear range between 2.00 × 10-6-9.00 × 10-5 mol L-1 and an LOD of 1.9 × 10-6 mol L-1 were obtained. The validation of both methods revealed good performance characteristics confirming applicability for the quantification of CTL in several pharmaceutical products. [ABSTRACT FROM AUTHOR]

Electroanalytical methods based on square-wave adsorptive-stripping voltammetry (SWAdSV) and flow-injection analysis with square-wave adsorptive-stripping voltammetric detection (FIA-SWAdSV) were developed for the determination of fluoxetine (FXT). The methods were based on the reduction of FXT at a mercury drop electrode at -1.2 V versus Ag/AgCl, in a phosphate buffer of pH 12.0, and on the possibility of accumulating the compound at the electrode surface. The SWAdSV method was successfully applied in the quantification of FXT in pharmaceutical products, human serum samples, and in drug dissolution studies. Because the presence of dissolved oxygen did not interfere significantly with the analysis, it was possible to quantify FXT in several pharmaceutical products using FIA-SWAdSV. This method enables analysis of up to 120 samples per hour at reduced costs. [ABSTRACT FROM AUTHOR]

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 - 1.25 V 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 1.0 × 10-7 and 2.0 × 10-6 molL-1 with a limit of detection of 5 × 10-8molL-1 for an accumulation time of 30s. 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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Few analytical methods are currently available for determination of apomorphine, the active substance of a new oral formulation used in the treatment of erectile dysfunction. In this way a flow injection electrochemical method (FIA-EC) was developed for its quantification and applied to pharmaceutical dosage forms. Based in previous findings regarding the stability of apomorphine in borate buIer and after optimization of several analytical parameters a single channel flow injection manifold was set up that enables the determination of this drug over the concentration range of 3 to 16 μmol L[SUP-1] with a detection limit of 0.5 μmol L[SUP-1] at a sampling rate of 90 h[SUP-1]. The simplicity and rapidity of the FIA-EC method used, its reproducibility and sensitivity make it suitable for quality control of pharmaceutical preparations of apomorphine intended for clinical use and research. [ABSTRACT FROM AUTHOR]

A square wave voltammetric (SWV) method and a flow injection analysis system with 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 system allowed 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%. [ABSTRACT FROM AUTHOR]

The electrochemical behaviour of the herbicide Asulam wets studied by cyclic and square wave voltammetry. Asulam may be irreversibly oxidised at a glassy carbon electrode. Maximum currents were obtained at pH = 1.9 in aqueous electrolyte solution. Based on the electrochemical behaviour of Asulam, two analytical methodologies were developed for its determination in water samples, using square wave voltammetry (SWV) and flow injection analysis (FIA) coupled with an amperometric detector. Limits of detection of 7.1 x 10[sup-6] molL[sup-1] and 1.2 x 10[sup-8] mol L[sup-1] for SWV and FIA respectively, were achieved. Repeatability was calculated by assessing the relative standard deviation (%) for 10 consecutive determinations of one sample. The found values were 2.1% for SWV and 5.0% for FIA. Validation of the results provided by SWV and FIA methodologies was performed by comparison with results from an HPLC-DAD technique. Good relative deviations were found (< 5%). Recovery trials were performed to assess the accuracy of the results and the obtained values were between 84% and 107% for both methods. [ABSTRACT FROM AUTHOR]

Indoor air quality at schools (elementary, primary) has been the subject of many studies; however, there are still relative few data regarding preschool (3- to 5-year-old children) environments. This investigation determined the concentrations of particulate matter (PM)2.5, total volatile organic compounds (TVOC), formaldehyde, carbon monoxide (CO), and ozone (O3) as well as the levels of carbon dioxide (CO2), temperature, and relative humidity (RH) in the indoor and outdoor air of two preschools situated in different geographical regions of Portugal. The indoor concentrations of TVOC, CO, O3, and CO2were predominantly higher at the end of school day compared to early morning periods. The TVOC and CO2concentrations were higher indoors than outdoors suggesting predominantly an indoor origin. Outdoor air infiltrations were the major contributing source of CO and O3to indoor air in both preschools. The concentrations of all pollutants were within the limits defined by national regulations and international organizations, except for TVOC that exceeded 8–12-fold higher than the recommendation of 0.2 mg/m3proposed by European Commission. The levels of CO2were below the protective guideline of 2250 mg/m3(Portuguese legislation); however, the observed ranges exceeded the Portuguese margin of tolerance (2925 mg/m3) at the end of school days, indicating the impact of occupancy rates particularly at one of the preschools. Regarding comfort parameters, temperature exerted a significant influence on O3concentrations, while RH values were significantly correlated with TVOC levels in indoor air of preschools, particularly during the late afternoon periods. [ABSTRACT FROM PUBLISHER]

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 +1.7 V versus AgCl/Ag, an irreversible process controlled by diffusion. Using a HMDE, a single cathodic peak is observed, at -1.0 V 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 µmol L-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. [ABSTRACT FROM AUTHOR]

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 -1.26 V 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. [ABSTRACT FROM AUTHOR]

An extraction-adsorptive stripping voltammetric procedure for the determination of the pesticide dialifos in soil samples using microwave-assisted solvent extraction and a mercury film ultramicroelectrode was developed. The method is based on the use of hexane-acetone solvent (1:1, v/v) and on controlled adsorptive accumulation of the insecticide at the potential of -0.10V (versus Ag/AgCl) in the presence of Britton-Robinson buffer (pH 2.0). Soil sample extracts were analyzed directly after drying and redissolution with the supporting electrolyte, but without other pretreatment. The limit of detection obtained for a 10 sec collection time was 2.0 µ 10 -8 mol L-1. Recovery experiments for the global procedure, at the 0.100 µg g-1 level, gave satisfactory average and standard deviation results for the two different soils tested. [ABSTRACT FROM AUTHOR]

An adsorptive stripping voltammetric procedure for the determination of the antidepressant venlafaxine in urine using a mercury film microelectrode was developed. The method is based on controlled adsorptive accumulation of the drug at the potential of −1.00 V (vs. Ag/AgCl) in the presence of 1.25 × 10−2 mol L−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 0.693 × 10−6 mol L−1. Recovery experiments gave good results at the 10−6 mol L−1 level (bias less 5% were obtained). [ABSTRACT FROM AUTHOR]

The aim of this study was to determine levels and risks due to inhalation exposure to polycyclic aromatic hydrocarbons (PAH) in different educational settings, namely for 3- to 5- year-old and 6- to 10-year-old children. Eighteen PAH (16 priority designated by US Environmental Protection Agency (USEPA) and dibenzo[a,l]pyrene and benzo[j]fluoranthene) were simultaneously collected in indoor and outdoor air at two Portuguese preschools (PS1–PS2) and five elementary schools (ES1–ES5) from March to May 2014. Indoor concentrations at PS and ES were significantly different, with total levels (∑PAHs) 0.721–15.9 ng/m3at PS1–PS2 and 5.03–23.6 ng/m3at ES1–ES5. The corresponding outdoor concentrations were, respectively, 1.22–32.7 ng/m3and 2.6–31.5 ng/m3. Polycyclic aromatic hydrocarbons with 2–3 aromatic rings were predominantly emitted by indoor sources, while compounds with 4–6 aromatic rings were mainly generated by infiltration of ambient PAH pollution to indoors. Excess lifetime risks of lung cancer exceeded the World Health Organization (WHO) designated guideline of 10–5in both types of schools (15–42-fold at PS; 15–52-fold at ES). However, total (sum of indoor and outdoor exposure) incremental lifetime cancer risks (ILCR) were below the USEPA level of 10–6at all studied institutions and thus considered negligible. Finally, ILCR due to indoor exposure represented 60–75% and 70–85% of the total ILCR at PS and ES, respectively, thus indicating the need for development and implementation of indoor air quality guidelines in educations settings. [ABSTRACT FROM PUBLISHER]

The Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method was applied to the extraction of 14 organochlorine pesticides (OCPs) residues from commercial fruit pulps available in supermarkets in Fortaleza, Northeastern Brazil. The analyses were carried out by gas chromatography (GC), coupled to an electron-capture detector (ECD), and were confirmed by GC-tandem mass spectrometry (MS). The parameters of the analytical method, such as accuracy, precision, linear range, limits of detection and quantification, were determined for each pesticide. The results showed good linearity (R2≥ 0.9916) and the overall average recoveries were considered satisfactory obtaining values between 69 and 110%, RSD of 2–15 %, except for hexachlorobenzene (HCB) in açai, acerola and guava pulp samples. The OCPs were detected in guava (α–HCH; lindane) and soursop (α, β–HCH isomers) samples. The QuEChERS method and GC–ECD were successfully used to analyze OCPs in commercially available Brazilian fruit pulps and can be applied in routine analytical laboratories. [ABSTRACT FROM AUTHOR]

Food allergens are a real threat to sensitized individuals. Although food labeling is crucial to provide information to consumers with food allergies, accidental exposure to allergenic proteins may result from undeclared allergenic substances by means of food adulteration, fraud or uncontrolled cross-contamination. Allergens detection in foodstuffs can be a very hard task, due to their presence usually in trace amounts, together with the natural interference of the matrix. Methods for allergens analysis can be mainly divided in two large groups: the immunological assays and the DNA-based ones. Mass spectrometry has also been used as a confirmatory tool. Recently, biosensors appeared as innovative, sensitive, selective, environmentally friendly, cheaper and fast techniques (especially when automated and/or miniaturized), able to effectively replace the classical methodologies. In this review, we present the advances in the field of food allergens detection toward the biosensing strategies and discuss the challenges and future perspectives of this technology. [ABSTRACT FROM PUBLISHER]

Eruca sativa(rocket salad) has been intensely consumed all over the world, insomuch as, this work was undertaken to evaluate the antioxidant status and the environmental contamination (positive and negative nutritional contribution) of leaves and stems from this vegetable. Antioxidant capacity of rocket salad was assessed by mean of optical methods, such as the total phenolic content (TPC), reducing power assay and DPPH radical scavenging activity. The extent of the environmental contamination was reached through the quantification of thirteen organochlorine pesticides (OCP) by using gas chromatography coupled with electron-capture detector (GC-ECD) and compound confirmations employing gas chromatography tandem mass-spectrometry (GC-MS/MS). The OCP residues were extracted by using Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) methodology.The extent of the environmental contamination was reached through the quantification of thirteen OCP by using gas chromatography coupled with electron-capture detector (GC-ECD) and compound confirmations employing GC-MS/MS. The OCP residues were extracted by using Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) methodology. This demonstrated that leaves presented more antioxidant activity than stems, emphasizing that leaves contained six times more polyphenolic compounds than stems. In what concerns the OCP occurrence, the average recoveries obtained at the three levels tested (40, 60 and 80 µg kg−1) ranged from 55% to 149% with a relative standard deviation of 11%, (except hexachrorobenzene). Three vegetables samples were collected from supermarkets and analysed following this study. According to data, only one sample achieved 16.21 of β-hexachlorocyclohexane, confirmed by GC-MS/MS. About OCP quantification, the data indicated that only one sample achieved 16.21 µg kg−1of β-hexachlorocyclohexane, confirmed by GC-MS/MS, being the QuEChERS a good choice for the of OCPs extraction. Furthermore, the leaves consumption guaranty higher levels of antioxidants than stems. [ABSTRACT FROM AUTHOR]

This study analysed 22 strawberry and soil samples after their collection over the course of 2 years to compare the residue profiles from organic farming with integrated pest management practices in Portugal. For sample preparation, we used the citrate-buffered version of the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. We applied three different methods for analysis: (1) 27 pesticides were targeted using LC-MS/MS; (2) 143 were targeted using low pressure GC-tandem mass spectrometry (LP-GC-MS/MS); and (3) more than 600 pesticides were screened in a targeted and untargeted approach using comprehensive, two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-TOF-MS). Comparison was made of the analyses using the different methods for the shared samples. The results were similar, thereby providing satisfactory confirmation of both similarly positive and negative findings. No pesticides were found in the organic-farmed samples. In samples from integrated pest management practices, nine pesticides were determined and confirmed to be present, ranging from 2 µg kg−1for fluazifop-p-butyl to 50 µg kg−1for fenpropathrin. Concentrations of residues in strawberries were less than European maximum residue limits. [ABSTRACT FROM AUTHOR]

Atmospheric pollution by motor vehicles is considered a relevant source of damage to architectural heritage. Thus the aim of this work was to assess the atmospheric depositions and patterns of polycyclic aromatic hydrocarbons (PAHs) in façades of historical monuments. Eighteen PAHs (16 PAHs considered by US EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in thin black layers collected from façades of two historical monuments: Hospital Santo António and Lapa Church (Oporto, Portugal). Scanning electron microscopy (SEM) was used for morphological and elemental characterisation of thin black layers; PAHs were quantified by microwave-assisted extraction combined with liquid chromatography (MAE-LC). The thickness of thin black layers were 80–110 μm and they contained significant levels of iron, sulfur, calcium and phosphorus. Total concentrations of 18 PAHs ranged from 7.74 to 147.92 ng/g (mean of 45.52 ng/g) in thin black layers of Hospital Santo António, giving a range three times lower than at Lapa Church (5.44–429.26 ng/g; mean of 110.25 ng/g); four to six rings compounds accounted at both monuments approximately for 80–85% of ∑PAHs. The diagnostic ratios showed that traffic emissions were significant source of PAHs in thin black layers. Composition profiles of PAHs in thin black layers of both monuments were similar to those of ambient air, thus showing that air pollution has a significant impact on the conditions and stone decay of historical building façades. The obtained results confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere. [ABSTRACT FROM AUTHOR]

A SPME-GC-MS/MS method for the determination of eight organophosphorus pesticides (azinphos-methyl, chlorpyriphos, chlorpyriphos-methyl, diazinon, fenitrothion, fenthion, malathion, and methidathion) in still and fortified wine was developed. The extraction procedure is simple, solvent free, and without any sample pretreatment. Limits of detection (LOD) and quantitation (LOQ) values in the range 0.1-14.3 µg/L and 0.2-43.3 µg/L, respectively, were obtained. The LOQ values are below the maximum residue levels (MRLs) established by European Regulation for grapes, with the exception of methidathion. Coefficients of correlation (R2) higher than 0.99 were obtained for the majority of the pesticides, in all different wines analyzed. [ABSTRACT FROM AUTHOR]

The evaluation of benzene in different environments such as indoor (with and without tobacco smoke), a city area, countryside, gas stations and near exhaust pipes from cars running on different types of fuels was performed. The samples were analyzed using gas chromatography (GC) with flame ionization detection (FID) and tandem mass spectrometric detection (MS/MS) (to confirm the identification of benzene in the air samples). Operating conditions for the GC-MS analysis were optimized as well as the sampling and sample preparation. The results obtained in this work indicate that i) the type of fuel directly influences the benzene concentration in the air. Gasoline with additives provided the highest amount of benzene followed by unleaded gasoline and diesel; ii) the benzene concentration in the gas station was always higher than the advisable limit established by law (5 μg m-3) and during the unloading of gasoline the achieved concentration was 8371 μg m-3; iii) the data from the countryside (Taliscas) and the urban city (Matosinhos) were below 5 μg m-3 except 5 days after a fire on a petroleum refinery plant located near the city; iv) it was proven that in coffee shops where smoking is allowed the benzene concentration is higher (6 μg m-3) than in coffee shops where this is forbidden (4 μg m-3). This method may also be helpful for environmental analytical chemists who use GC-MS/MS for the confirmation or/and quantification of benzene. [ABSTRACT FROM AUTHOR]

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 µg kg-1 in each pesticide. The pesticide residues were extracted using 20 mL acetonitrile at 60°C, 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 µg kg-1 for carbaryl to 12.3 µg kg-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. [ABSTRACT FROM AUTHOR]

Seven pyrethroids (bifenthrin, fenpropathrin, λ-cyhalothrin, permethrin, α-cypermethrin, fenvalerate, and deltamethrin) were extracted from water using C18 solid-phase extraction disks, followed by gas chromatography with an electron capture detector (GC-ECD) analysis. The limits of detection in water samples ranged from 0.5 ng L-1 (fenpropathrin) to 110 ng L-1 (permethrin), applying the calibration graph. The effects of different numbers of (re)utilizations of the same disks (up to four times with several concentrations) on the recoveries of the pyrethroids were considered. The recoveries were all between 70 and 120% after four utilizations of the same disk. There was no difference between these recoveries at a confidence level of 95%. [ABSTRACT FROM AUTHOR]

An analytical method, based on microwave-assisted extraction and liquid chromatography with diode array detection, for the determination of six carbamate and three urea pesticides in fresh and processed tomato samples is described. Significant parameters affecting extraction efficiency were optimized. Under optimum microwave-assisted extraction conditions (20 mL acetonitrile, for 10 minutes, at 60°C), pesticides were extracted with recoveries ranging from 57.6 to 102% (RSDs < 7%). Quantification limits between 6.5 and 39.6 µg/kg were obtained. A total number of 28 different fresh tomato samples and 6 processed tomato products were analysed. Confirmation of suspicious samples was performed by LC-MS. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

A simple, rapid, and precise amperometric method for quantification of N-methylcarbamate pesticides in water samples and phytopharmaceuticals is presented. Carbofuran and fenobucarb are the target analytes. The method is developed in flow conditions providing the anodic oxidation of phenolic-based compounds formed after alkaline hydrolysis. Optimization of instrumental and chemical variables is presented. Under the optimal conditions, the amperometric signal is linear for carbofuran and fenobucarb concentrations over the range of 1.0 × 10-7 to 1.0 × 10-5 mol L-1, with a detection limit of about 2 ng mL-1. The amperometric method is successfully applied to the analysis of spiked environmental waters and commercial formulations. The proposed method allows 90 samples to be analysed per hour, using 500 µL of sample, and producing wastewaters of low toxicity. The proposed method permits determinations at the µg L-1 level and offers advantages of simplicity, accuracy, precision, and applicability to coloured and turbid samples, and automation feasibility. [ABSTRACT FROM AUTHOR]

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 μ g/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. [ABSTRACT FROM AUTHOR]

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 3.0×10-8 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 by MASE-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. [ABSTRACT FROM AUTHOR]

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 1.0×10 -4 to 8.0×10 -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 –1.00 V vs. AgCl/Ag in a large range of pH with higher signal at pH 7.0. Linearity was obtained in 4.2×10 -6 and 9.4×10 -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 +0.75 V 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 1.0×10 -7 and 1.0×10 -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%. [ABSTRACT FROM AUTHOR]

Microwave-assisted solvent extraction was combined with anodic adsorptive stripping voltammetry at a gold microelectrode to extract and quantify the herbicide atrazine in spiked soil samples. A systematic study of the experimental parameters affecting the stripping response was carried out by square-wave voltammetry. The voltammetric procedure is based on controlled adsorptive accumulation of atrazine at the potential of 0.35 V(versus Ag/AgCl) in the presence of Britton–Robinson buffer pH(2.0). The limit of detection obtained for a 30 sec collection time was 4.3 × 10−7 mol L−1. Recovery experiments, at the 1 µg g−1 level of spiking, gave good results for the global procedure, and the values found were comparable to those obtained by HPLC. [ABSTRACT FROM AUTHOR]