Selective solid-phase extraction of organophosphorus pesticides and their oxon-derivatives from water samples using molecularly imprinted polymer followed by high-performance liquid chromatography with UV detection.

A molecularly imprinted polymer was synthesized and characterized to be used as solid-phase extraction sorbent for simultaneous chlorpyrifos and diazinon and their oxon derivatives. Several imprinted polymers were prepared and evaluated in a retention study of these analytes compared with a non-printed polymer. Several parameters affecting the extraction of imprinted polymer such as washing solvent, composition and volume of the eluting solvent and sample volume, were also investigated. Under the optimum conditions, the developed method provided satisfactory limits of detection ranging between 0.07 µg L-1 to 0.12 µg L-1 and the material showed an excellent reusability (> 50 reuses). The method was applied to the extraction and preconcentration of these analytes in water samples. The average recoveries ranged from 79 ± 6 to 104 ± 3 %.

Sol-gel molecularly imprinted polymer for selective solid phase microextraction of organophosphorous pesticides.

A sol-gel technique was applied for the preparation of water-compatible molecularly imprinted polymer (MIP) for solid phase microextraction (SPME) using diazinon as template and polyethylene glycol as functional monomer. The MIP-coated fiber demonstrated much better selectivity to diazinon and its structural analogs in aqueous cucumber sample than in distilled water, indicating its potential in real samples. Thanks to its specific adsorption as well as rough and porous surface, the coating revealed rather larger extraction capability than the non-imprinted polymer and commercial fibers. In addition, the fiber exhibited excellent thermal (about 350°C) and chemical stability (organic and inorganic). After optimization of several parameters affecting extraction efficiency, a method based on MIP-SPME combined with gas chromatography was developed for the determination of organophosphorus pesticides (OPPs) in vegetable samples. The limits of detection for the tested OPPs were in the range of 0.017-0.77 µg kg(-1). The proposed method was applied to evaluate OPPs in spiked cucumber, green pepper, Chinese cabbage, eggplant and lettuce samples, and recoveries of 81.2-113.5% were obtained by the standard addition method with three spiking levels in each kind of vegetable.

Desorption of two organophosphorous pesticides from soil with wastewater and surfactant solutions.

A batch test was used to evaluate the extent of desorption of diazinon and dimethoate, preadsorbed on a calcareous agricultural soil, representative of the Mediterranean area. Urban wastewater from a secondary treatment and seven surfactant solutions, at concentrations ranging from 0.75 mg L(-1) to 10 gL(-1), were used. The surfactants assayed were cationic (hexadecyl trimethyl ammonium bromide (HD)), anionic (sodium dodecyl sulfate (SDS), Aerosol 22 (A22) and Biopower (BP)), and nonionic (Tween 80 (TW), Triton X 100 (TX) and Glucopon 600 (G600)). Desorption of dimethoate was either not affected or only slightly by the nonionic and anionic surfactants tested, while desorption of diazinon from the soil was only enhanced by A22, BP and TW. This desorption increase correlated significantly with the surfactant concentration of the solution used for desorption and with the concurrent increase in the supernatant of the dissolved organic carbon, in particular that originating from the surfactant. This parameter did not vary with the use of SDS, G600 and TX. The cationic surfactant HD was retained on the soil surface, as confirmed by an increase in soil organic carbon, resulting in a fall in desorption rate for both pesticides. Comparing treatment by wastewater with control water, there was no difference in desorption rate for either pesticide. Mixed TW/anionic surfactant solutions either did not modify or slightly increased desorption of both pesticides in comparison with individual surfactant solutions.

Subcritical water extraction to evaluate desorption behavior of organic pesticides in soil.

We evaluated the feasibility of extracting organic pesticides in soil using a hot-water percolation apparatus at 105 degrees C and 120 kPa pressure. Efficiency of the method was assessed by extracting six selected pesticides (acetochlor, atrazine, diazinon, carbendazim, imidacloprid, and isoproturon) from previously equilibrated soil at 13.6-65.8 mg/kg concentration range. Studies were performed on brown forest soil with clay alluviation (Luvisol). The method developed was compared to the traditional batch equilibrium method in terms of desorbed amount of pesticides from soil and extraction time. Pesticides in the liquid phase from the batch sorption experiment and in the effluent from the hot-water percolation were quantified by high-performance liquid chromatography with UV detection. The results of the percolation experiment are in close correlation with those of the conventional soil testing method. Desorbed quantities by hot-water percolation were 85% acetochlor, 62% atrazine, 65% carbendazim, 44% diazinon, 95% imidacloprid, and 84% isoproturon, whereas using batch equilibrium method 101, 66, 64, 37, 81, and 90% were desorbed, expressed as the percentage of the adsorbed amount of pesticide on soil following equilibration. The average time for hot-water extraction was 3.45 min, in contrast to the 16 h time consumption of the traditional batch method. The effect of temperature on stability of selected compounds was also evaluated using pesticide-spiked sand without soil. Recoveries of analytes ranged between 84.6 and 91.1% with reproducibility of 7.9-10.2%, except for diazinon, for which recovery was 59.4% with 14.4% relative standard deviation since decomposition occurred at elevated temperature. The percolation process has been described by a first-order kinetic equation. The parameters calculated from the equation provide an opportunity to estimate the amount of compound available for desorption, the rate of desorption processes in the studied soil-pesticide-water system, and modeling the leaching process to obtain additional information on the environmental behavior of the examined pesticide.