Fe3 O4 nanoparticles coated with polyhedral oligomeric silsesquioxanes and ß-cyclodextrin for magnetic solid-phase extraction of carbaryl and carbofuran.

In this study, porous sandwich structure Fe3 O4 nanoparticles coated by polyhedral oligomeric silsesquioxanes and ß-cyclodextrin were prepared by surface polymerization and were used as the magnetic solid phase extraction adsorbent for the extraction and determination of carbaryl and carbofuran. The Fe3 O4 nanoparticles coated with polyhedral oligomeric silsesquioxanes and ß-cyclodextrin were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, vibrating sample magnetometry, and scanning electron microscopy. After optimizing the extraction conditions, a method that combined magnetic solid phase extraction with high-performance liquid chromatography was developed for the determination of carbaryl and carbofuran in apple. The method exhibited a good linearity in the range of 2-400 µg/kg for carbaryl and carbofuran (R2  = 0.9995), respectively. The limits of detection were 0.5 µg/kg of carbaryl and 0.7 µg/kg for carbofuran in apple, respectively. Extraction recoveries ranged from 94.2 to 103.1% with the preconcentration factor of 300 and the relative standard deviations were less than 5.9%. These results indicated that the method combined magnetic solid phase extraction with high-performance liquid chromatography and was promising for the determination of carbaryl and carbofuran at trace amounts.

Synthesis and Application of Novel Molecularly Imprinted Solid Phase Extraction Materials Based on Carbon Nanotubes for Determination of Carbofuran in Human Serum by High Performance Liquid Chromatography.

Novel molecularly imprinted polymers (MIPs) based on multiwalled carbon nanotubes (MWNTs) were synthesized using carbofuran as template, methacrylic acid as functional monomer, and trimethylolpropane trimethacrylate as cross-liking agent, respectively. Characterization results showed that the carbofuran MIPs have been successfully grafted onto the surface of MWNTs as a thin layer with high stability. The results of adsorption dynamics indicated that the synthesized MWNT-MIPs displayed a biphase adsorption profile and good selective recognition to carbofuran with equilibrium adsorption of 106.2 mg/g. The MWNTs-MIPs synthesized were further applied as the adsorbent material of solid-phase extraction (SPE) for the pretreatment of carbofuran in human serum, analyzed using high performance liquid chromatograph (HPLC). The recoveries obtained ranged from 89.0 ± 4.8 to 93.6 ± 3.2, showing that the MWNTs-MIPs-SPE system developed have specific recognition toward carbofuran. Results above indicated that the proposed system filled with synthesized MWNTs-MIPs provided a fast and selective extraction of carbofuran in serum.

N-methylcarbamate pesticides and their phenolic degradation products: hydrolytic decay, sequestration and metal complexation studies.

We report on the rates of decomposition of a group of N-methylcarbamate (NMC) pesticides (carbaryl, carbofuran and propoxur) under pre-determined tropical field conditions. Rates of decomposition for three NMCs were determined at pH 7.08 and T = 20 °C and pH 7.70 and T = 33 °C respectively, as follows: carbaryl (78 days and 69 days); carbofuran (143 days and 83 days) and propoxur (116 days and 79 days). Investigation on methods for removal of NMCs and their phenolic decomposition products shows that activated charcoal outperforms zeolite, alumina, diatomaceous earth, cellulose and montmorillonite clay in the removal of both NMCs and phenols from aqueous solution. Furthermore, metal complexation studies on the NMCs and phenols showed that Fe (III) forms a complex with isopropoxyphenol (IPP) within which the Fe:IPP ratio is 1:3, indicative of the formation of a metal chelate complex with the formula Fe(IPP)3.

Selective amperometric flow-injection analysis of carbofuran using a molecularly-imprinted polymer and gold-coated-magnetite modified carbon nanotube-paste electrode.

Herein, we propose a new approach for selective determination of carbofuran (CBF) in vegetables, based on a simple flow-injection system using a molecularly-imprinted amperometric sensor. The sensor design is based on a carbon-paste electrode decorated with carbon nanotubes and gold-coated magnetite (CNTs-Fe3O4@Au/CPE) coated with a molecularly-imprinted polymer (MIP) for CBF sensing. The MIP was synthesized on the electrode surface by electropolymerization using a supramolecular complex, namely 4-ter-butylcalix [8] arene-CBF (4TB[8]A-CBF), as the template. We used o-phenylenediamine as the functional monomer. Our results demonstrate that incorporation of the MIP coating improves the electrochemical catalytic properties of the electrode, increases its surface area, and increases CBF selectivity by modulating the electrical signal through elution and re-adsorption of CBF. The imprinted sensor (MIP-CNTs-Fe3O4@Au/CPE) was used in a flow-injection analysis (FIA) system. Experimental conditions were investigated in amperometric mode, with the following optimized parameters: phosphate buffer solution (0.1M, pH 8.0) as the carrier, flow rate 0.5mLmin-1, applied potential +0.50V. When used in the FIA system, the designed imprinted sensor yields a linear dynamic range for CBF from 0.1 to 100µM (r2 = 0.998) with a detection limit of 3.8nM (3Sb), and a quantification limit of 12.7nM (10Sb). The sensor exhibits acceptable precision (%RSD = 4.8%) and good selectivity toward CBF. We successfully applied the electrode to detect CBF in vegetable samples.

Carbofuran removal in continuous-photocatalytic reactor: Reactor optimization, rate-constant determination and carbofuran degradation pathway analysis.

Carbofuran (CBF) removal in a continuous-flow photocatalytic reactor with granular activated carbon supported titanium dioxide (GAC-TiO2) catalyst was investigated. The effects of feed flow rate, TiO2 concentration and addition of supplementary oxidants on CBF removal were investigated. The central composite design (CCD) was used to design the experiments and to estimate the effects of feed flow rate and TiO2 concentration on CBF removal. The outcome of CCD experiments demonstrated that reactor performance was influenced mainly by feed flow rate compared to TiO2 concentration. A second-order polynomial model developed based on CCD experiments fitted the experimental data with good correlation (R2 ∼ 0.964). The addition of 1 mL min-1 hydrogen peroxide has shown complete CBF degradation and 76% chemical oxygen demand removal under the following operating conditions of CBF ∼50 mg L-1, TiO2 ∼5 mg L-1 and feed flow rate ∼82.5 mL min-1. Rate constant of the photodegradation process was also calculated by applying the kinetic data in pseudo-first-order kinetics. Four major degradation intermediates of CBF were identified using GC-MS analysis. As a whole, the reactor system and GAC-TiO2 catalyst used could be constructive in cost-effective CBF removal with no impact to receiving environment through getaway of photocatalyst.

Ecotoxicological analysis during the removal of carbofuran in fungal bioaugmented matrices.

Biomixtures are used for the removal of pesticides from agricultural wastewater. As biomixtures employ high content of lignocellulosic substrates, their bioaugmentation with ligninolytic fungi represents a novel approach for their enhancement. Nonetheless, the decrease in the concentration of the pesticide may result in sublethal concentrations that still affect ecosystems. Two matrices, a microcosm of rice husk (lignocellulosic substrate) bioaugmented with the fungus Trametes versicolor and a biomixture that contained fungally colonized rice husk were used in the degradation of the insecticide/nematicide carbofuran (CFN). Elutriates simulating lixiviates from these matrices were used to assay the ecotoxicological effects at sublethal level over Daphnia magna (Straus) and the fish Oreochromis aureus (Steindachner) and Oncorhynchus mykiss (Walbaum). Elutriates obtained after 30 d of treatment in the rice husk microcosms at dilutions over 2.5% increased the offspring of D. magna as a trade-off stress response, and produced mortality of neonates at dilutions over 5%. Elutriates (dilution 1:200) obtained during a 30 d period did not produce alterations on the oxygen consumption and ammonium excretion of O. mykiss, however these physiological parameters were affected in O. aureus at every time point of treatment, irrespective of the decrease in CFN concentration. When the fungally colonized rice husk was used to prepare a biomixture, where more accelerated degradation is expected, similar alterations on the responses by O. aureus were achieved. Results suggest that despite the good removal of the pesticide, it is necessary to optimize biomixtures to minimize their residual toxicity and potential chronic effects on aquatic life.

Design of an optimized biomixture for the degradation of carbofuran based on pesticide removal and toxicity reduction of the matrix.

Pesticide biopurification systems contain a biologically active matrix (biomixture) responsible for the accelerated elimination of pesticides in wastewaters derived from pest control in crop fields. Biomixtures have been typically prepared using the volumetric composition 50:25:25 (lignocellulosic substrate/humic component/soil); nonetheless, formal composition optimization has not been performed so far. Carbofuran is an insecticide/nematicide of high toxicity widely employed in developing countries. Therefore, the composition of a highly efficient biomixture (composed of coconut fiber, compost, and soil, FCS) for the removal of carbofuran was optimized by means of a central composite design and response surface methodology. The volumetric content of soil and the ratio coconut fiber/compost were used as the design variables. The performance of the biomixture was assayed by considering the elimination of carbofuran, the mineralization of (14)C-carbofuran, and the residual toxicity of the matrix, as response variables. Based on the models, the optimal volumetric composition of the FCS biomixture consists of 45:13:42 (coconut fiber/compost/soil), which resulted in minimal residual toxicity and ∼99% carbofuran elimination after 3 days. This optimized biomixture considerably differs from the standard 50:25:25 composition, which remarks the importance of assessing the performance of newly developed biomixtures during the design of biopurification systems.

Electrochemical biosensor for carbofuran pesticide based on esterases from Eupenicillium shearii FREI-39 endophytic fungus.

In this work, a biosensor was constructed by physical adsorption of the isolated endophytic fungus Eupenicillium shearii FREI-39 esterase on halloysite, using graphite powder, multi-walled carbon nanotubes and mineral oil for the determination of carbofuran pesticide by inhibition of the esterase using square-wave voltammetry (SWV). Specific esterase activities were determined each 2 days over a period of 15 days of growth in four different inoculation media. The highest specific activity was found on 6th day, with 33.08 U on PDA broth. The best performance of the proposed biosensor was obtained using 0.5 U esterase activity. The carbofuran concentration response was linear in the range from 5.0 to 100.0 µg L(-1) (r=0.9986) with detection and quantification limits of 1.69 µg L(-1) and 5.13 µg L(-1), respectively. A recovery study of carbofuran in spiked water samples showed values ranging from 103.8±6.7% to 106.7±9.7%. The biosensor showed good repeatability and reproducibility and remained stable for a period of 20 weeks. The determination of carbofuran in spiked water samples using the proposed biosensor was satisfactory when compared to the chromatographic reference method. The results showed no significant difference at the 95% confidence level with t-test statistics. The application of enzymes from endophytic fungi in constructing biosensors broadens the biotechnological importance of these microorganisms.

Application of an optimized dispersive nanomaterial ultrasound-assisted microextraction method for preconcentration of carbofuran and propoxur and their determination by high-performance liquid chromatography with UV detection.

An extraction method based on dispersive nanomaterial ultrasound-assisted microextraction was used for the preconcentration of carbofuran and propoxur insecticides in water samples prior to high-performance liquid chromatography with UV detection. ZnS:Ni nanoparticles were synthesized based on the reaction of the mixture of zinc acetate and nickel acetate with thioacetamide in aqueous media and then loaded on activated carbon (ZnS:Ni-AC). Different methods were used for recognizing the properties of ZnS:Ni-AC and then this nanomaterial was used for extraction of carbamate insecticide as new adsorbent. The influence of variables on the extraction method (such as amount of adsorbent (mg: NiZnS-AC), pH and ionic strength of sample solution, vortex and ultrasonic time (min), ultrasound temperature and desorption volume (mL) was investigated by a screening 2(7-4) Plackett-Burman design. Then the significant variables were optimized by using a central composite design combined with a desirability function. At optimum conditions, this method had linear response >0.0060-10 µg/mL with detection limit 0.0015 µg/mL and relative standard deviations <5.0% (n = 3).

Influence of different abiotic and biotic factors on the metalaxyl and carbofuran dissipation.

Metalaxyl and carbofuran dissipation was studied in response to different factors (soil bacterial communities, light irradiation, presence of an inorganic culture medium and presence of soil) and combinations of these factors in short-term experiments (48 h). The soil microbial communities have no effect on metalaxyl or carbofuran dissipation in the time scale employed. Light irradiation and soil promote metalaxyl and carbofuran dissipation by photodegradation and adsorption, respectively. However, photodegradation has a stronger effect on metalaxyl and carbofuran dissipation than the adsorption of the pesticides in the soil. The addition of the culture medium have no direct effect on pesticide dissipation, degradation by microbial communities or adsorption but its presence greatly increased photodegradation.

Selection of support materials for immobilization of Burkholderia cepacia PCL3 in treatment of carbofuran-contaminated water.

This study investigated the utilization of agricultural matrices as the support materials for cell immobilization to improve the technique of bioremediation. Coir, bulrush, banana stem and water hyacinth stem in both delignified and undelignified forms were used to immobilize Burkholderia cepacia PCL3 in bioremediation of carbofuran at 5 mg l(-1) in synthetic wastewater. Undelignified coir was found to be the most suitable support material for cell immobilization, giving the short half-life of carbofuran of 3.40 d (2.8 times shorter than the treatments with free cells). In addition, it could be reused three times without a loss in ability to degrade carbofuran. The growth and degradation ability of free cells were completely inhibited at the initial carbofuran concentrations of 250 mg l(-1), while there was no inhibitory effect of carbofuran on the immobilized cells. The results indicated a great potential for using the agricultural matrices as support material for cell immobilization to improve the overall efficiency of carbofuran bioremediation in contaminated water by B. cepacia PCL3.

Determination of N-methylcarbamate insecticides in water samples using dispersive liquid-liquid microextraction and HPLC with the aid of experimental design and desirability function.

A rapid and simple method for the extraction and preconcentration of N-methylcarbamates (NMCs) (carbofuran, carbaryl and promecarb) in water samples using dispersive liquid-liquid microextraction (DLLME) using chemometrics was developed. Influence variables such as volume of extracting (CHCl(3)) and dispersing solvents (ACN), pH and ionic strength, extraction time and centrifugation time and speed were screened in a 2(7-4) Plackett-Burman design was investigated. The significant variables were optimized by using a central composite design (CCD) combined with desirability function (DF). At optimum conditions values of variables set as 126 µL chloroform, 1.5 mL acetonitrile, 1 min extraction time, 10 min centrifugation at 4000 rpm min(-1), natural pH, 4.7% (w/v) NaCl, the separation was reached in less than 14 min using a C(18) column and an isocratic binary mobile phase (acetonitrile: water (50:50, v/v)) with flow rate of 1.0 mL min(-1). At optimum conditions method has linear response over 0.001-10 µg mL(-1) with detection limit between 0.0001 and 0.0005 µg mL(-1) with relative standard deviations (RSDs) in the range 2.18-5.06% (n=6).

Adsorption and desorption kinetics of carbofuran in acid soils.

Carbofuran adsorption and desorption were investigated in batch and stirred flow chamber (SFC) tests. The carbofuran adsorption capacity of the soils was found to be low and strongly dependent on their clay and organic carbon contents. Carbofuran sorption was due mainly (>80%) to fast adsorption processes governed by intraparticle diffusion. The adsorption kinetic constant for the pesticide ranged from 0.047 to 0.195 min(-1) and was highly correlated with constant n in the Freundlich equation (r=0.965, P<0.05). Batch tests showed carbofuran desorption to be highly variable and negatively correlated with eCEC and the clay content. The SFC tests showed that soil organic carbon (C) plays a key role in the irreversibility of carbofuran adsorption. Carbofuran desorption increased rapidly at C contents below 4%. The desorption kinetic constant for the compound (0.086-0.195 min(-1)) was generally higher than its adsorption kinetic constant; therefore, carbofuran is more rapidly desorbed than it is adsorbed in soil.

Determination of pesticides in surface and ground waters by liquid chromatography-electrospray-tandem mass spectrometry.

The sensitive multiresidual analytical method for simultaneous analysis of 14 most commonly used agricultural pesticides in Serbia was developed and optimized. The selected insecticides, fungicides and herbicides belong to seven chemical classes (organophosphates, neonicotinoids, carbamates, diacylhydrazines, benzimidazoles, triazines and phenylureas). The method was based on solid-phase extraction followed by liquid chromatography-tandem mass spectrometry. The following parameters that may affect the SPE procedure efficiency were optimized: the sorbent type in combination with different elution solvents, the sample pH and the sample volume. For each pesticide, MS(n) analysis was performed and distinctive ions and transitions were selected for identification and quantification, as well as for confirmation purposes. External matrix-matched calibration method was used to eliminate variable matrix effect and ensure precise quantification. Good recoveries (72-129%), and low limits of detection (0.4-5.5 ng L(-1)) and quantification (1.1-18.2 ng L(-1)) were achieved for all selected pesticides. The developed and optimized method was successfully applied in the analysis of several river waters, as well as ground waters in Serbia, influenced by agriculture. The most frequently detected pesticide was carbendazim. Dimethoate, carbofuran and propazine were also found in the investigated samples.

Validation of method for determination of different classes of pesticides in aqueous samples by dispersive liquid-liquid microextraction with liquid chromatography-tandem mass spectrometric detection.

In this study, a simple, rapid and efficient method has been developed for the extraction and preconcentration of different classes of pesticides, carbofuran (insecticide), clomazone (herbicide) and tebuconazole (fungicide) in aqueous samples by dispersive liquid-liquid microextraction (DLLME) coupled with liquid chromatography-tandem mass spectrometric detection. Some experimental parameters that influence the extraction efficiency, such as the type and volume of the disperser solvents and extraction solvents, extraction time, speed of centrifugation, pH and addition of salt were examined and optimized. Under the optimum conditions, the recoveries of pesticides in water at spiking levels between 0.02 and 2.0 microg L(-1) ranged from 62.7% to 120.0%. The relative standard deviations varied between 1.9% and 9.1% (n=3). The limits of quantification of the method considering a 50-fold preconcentration step were 0.02 microg L(-1). The linearity of the method ranged from 1.0 to 1000 microg L(-1) for all compounds, with correlation coefficients varying from 0.9982 to 0.9992. Results show that the method we propose can meet the requirements for the determination of pesticides in water samples. The comparison of this method with solid-phase extraction indicates that DLLME is a simple, fast, and low-cost method for the determination of pesticides in natural waters.

Removal of insecticide carbofuran from aqueous solutions by banana stalks activated carbon.

In this work, activated carbon was prepared from banana stalks (BSAC) waste to remove the insecticide carbofuran from aqueous solutions. The effects of contact time, initial carbofuran concentration, solution pH and temperature (30, 40 and 50 degrees C) were investigated. Adsorption isotherm, kinetics and thermodynamics of carbofuran on BSAC were studied. Equilibrium data were fitted to the Langmuir, Freundlich and Temkin isotherm models and the data best represented by the Langmuir isotherm. Thermodynamic parameters such as standard enthalpy (DeltaH(o)), standard entropy (DeltaS(o)) and standard free energy (DeltaG(o)) were evaluated. Regeneration efficiency of spent BSAC was studied using ethanol as a solvent. The efficiency was found to be in the range of 96.97-97.35%. The results indicated that the BSAC has good regeneration and reusability characteristics and can be used as alternative to present commercial activated carbon.

[Determination of carbofuran residue in aquatic products by gas chromatography].

A capillary gas chromatographic (GC) method was developed for the determination of carbofuran residue in aquatic products (Ctenopharyngodon idellus and Penaens vannamei). The sample was extracted with acetonitrile, defatted by hexane, re-extracted by acetoacetate and cleaned up with a Al2O3 column, and then determined by GC. The standard curve was linear in the investigated range of 0.1 - 10.0 mg/L. The correlation coefficients were more than 0.999 5, the recoveries were 78% - 90% with the relative standard deviations of 2.49% -9.59% at the spiking levels of 0.02 - 10.0 mg/kg. The detection limit of carbofuran was 0.02 mg/kg.

The removal efficiency of chestnut shells for selected pesticides from aqueous solutions.

The removal of selected pesticides such as carbofuran (CF) and methyl parathion (MP) using low-cost abundant sorbent chestnut shells from aqueous solutions has been investigated in the present study. The sorption parameters, i.e., contact time, pH, initial pesticide solution concentration and temperature have been studied. Maximum percent sorption (99+/-1%) was achieved for (0.38-3.80) x10(-4) and (0.45-4.5) x10(-4) mol dm(-3) of MP and CF pesticide solutions respectively, using 0.4 g of sorbent in 100 ml of solution for 30 min agitation time at pH 6. The Freundlich, Langmuir and Dubinin-Radushkevich (D-R) models have been applied, and their constants for methyl parathion and carbofuran, sorption intensity 1/n (0.55+/-0.02 and 0.54+/-0.04), multilayer sorption capacity C(m) (28.3+/-0.5 and 16.4+/-0.7) x10(-3) mol l(1-1/n)dm(3/n)g(-1), monolayer sorption capacity Q (22.5+/-0.5 and 10.8+/-0.3) x10(-6) mo lg(-1), binding energy, b (2.9+/-0.2 and 5.2+/-0.5) x10(4) dm(3)mol(-1), and sorption energy E (11.2+/-0.1 and 11.5+/-0.2 kJ mol(-1)) have been evaluated respectively. Lagergren, Morris-Weber and Reichenberg equations were employed to study kinetics of sorption process. Thermodynamic parameters DeltaH (-5.09+/-0.1 and 22.8+/-0.4 kJ mol(-1)), DeltaS (-4.33+/-0.0003 and 0.09+/-0.001 kJ mol(-1)K(-1)) and DeltaG((303K)) (-2.9 and -3.8 kJ mol(-1)) have been calculated for methyl parathion and carbofuran, respectively. The developed sorption procedure has been employed to environmental samples.

Adsorption of 2,4-D and carbofuran pesticides using fertilizer and steel industry wastes.

The removal of 2,4-dichlorophenoxyacetic acid (2,4-D) and carbofuran from aqueous solution was studied by using fertilizer industry waste (carbon slurry) and steel industry wastes (blast furnace slag, dust, and sludge) as adsorbents in batch. Adsorption was found to be in decreasing order: carbon slurry, blast furnace sludge, dust, and slag, respectively. Carbonaceous adsorbent prepared from carbon slurry exhibited the uptake capacity of 212 and 208 mg g(-1) for 2,4-D and carbofuran, respectively at 25 degrees C and pH 7.5. Adsorption equilibrium, kinetics, and thermodynamics were investigated as a function of initial pH, temperature, and pesticide concentrations. Equilibrium data fitted well to the Langmuir equilibrium model in the studied concentration range of 2,4-D and carbofuran at all the temperatures studied. Two simplified models, including pseudo-first-order and pseudo-second-order kinetic models, were used to test the adsorption kinetics. Adsorption of 2,4-D and carbofuran on carbon slurry at 25, 35, and 45 degrees C could be best fitted in the pseudo-second-order kinetic model. Pore diffusion was confirmed as the essential rate-controlling step with the help of Bangham's equation.

[Forensic chemical detection of furadan].

Isolation of furadan from biological material by ethyl acetate is considered. Column chromatography with silicone gel L 100/160micro was used to purify extractions from biological objects. A technique was elaborated for identification and quantitation of furadan in cadavers. It is possible to use this technique in forensic expert examination.