Chemometric assisted ultrasound leaching-solid phase extraction followed by dispersive-solidification liquid-liquid microextraction for determination of organophosphorus pesticides in soil samples.

Ultrasound leaching-solid phase extraction (USL-SPE) followed by dispersive-solidification liquid-liquid microextraction (DSLLME) was developed for preconcentration and determination of organophosphorus pesticides (OPPs) in soil samples prior gas chromatography-mass spectrometry analysis. At first, OPPs were ultrasonically leached from soil samples by using methanol. After centrifugation, the separated methanol was diluted to 50 mL with double-distillated water and passed through the C18 SPE cartridge. OPPs were eluted with 1 mL acetonitrile. Thus, 1 mL acetonitrile extract (disperser solvent) and 10 µL 1-undecanol (extraction solvent) were added to 5 mL double-distilled water and a DSLLME technique was applied. The variables of interest in the USL-SPE-DSLLME method were optimized with the aid of chemometric approaches. First, in screening experiments, fractional factorial design (FFD) was used for selecting the variables which significantly affected the extraction procedure. Afterwards, the significant variables were optimized using response surface methodology (RSM) based on central composite design (CCD). Under the optimum conditions, the enrichment factors were 6890-8830. The linear range was 0.025-625 ng g(-1) and limits of detection (LODs) were between 0.012 and 0.2 ng g(-1). The relative standard deviations (RSDs) were in the range of 4.06-8.9% (n=6). The relative recoveries of OPPs from different soil samples were 85-98%.

Determination of abamectin in citrus fruits using SPE combined with dispersive liquid-liquid microextraction and HPLC-UV detection.

A new pretreatment method, SPE combined with dispersive liquid-liquid microextraction, was proposed for the determination of abamectin in citrus fruit samples for the first time. In this method, fruit samples were extracted by ultrasound-assisted extraction followed by SPE. Then, the SPE was used as a disperser solvent in the next dispersive liquid-liquid microextraction step for further purification and enrichment of abamectin. The effects of various parameters on the extraction efficiency of the proposed method were investigated and optimized. Good linearity of abamectin was obtained from 0.005 to 10.0 mg/kg for B1a and from 0.05 to 10.0 mg/kg for B1b with correlation coefficient (r(2)) of 0.998 for B1a and 0.991 for B1b, respectively. The LODs were 0.001 and 0.008 mg/kg (S/N = 3) for B1a and B1b, respectively. The relative recoveries at three spiked levels were ranged from 87 to 96% with the RSD less than 11% (n = 3). The method has been successfully applied to the determination of abamectin in citrus fruit samples.

Comparison of ultrasound-assisted emulsification and dispersive liquid-liquid microextraction methods for the speciation of inorganic selenium in environmental water samples using low density extraction solvents.

Herein, ultrasound-assisted emulsification microextraction (USAEME) and dispersive liquid-liquid microextraction (DLLME) methods based on applying low-density organic solvents have been critically compared for the speciation of inorganic selenium, Se(IV) (selenite) and Se(VI) (selenate) in environmental water samples by gas chromatography-flame ionization detection (GC-FID). At pH 2 and T=75°C for 7 min, only Se(IV) was able to form the piazselenol complex with 4-nitro-o-phenylenediamine. Piazselenol was extracted using an extraction solvent and was injected into a GC-FID instrument for the determination of Se(IV). Conveniently, Se(VI) remained in the aqueous phase. Total inorganic selenium was determined after the reduction of Se(VI) to Se(IV) and prior to the above procedures. The Se(VI) concentration was calculated as the difference between the measured total inorganic selenium and Se(IV) content. The effect of various experimental parameters on the efficiencies of the two methods and their optimum values were studied with the aid of response surface methodology and experimental design. Under the optimal conditions, the limit of detections (LODs) for Se(IV) obtained by USAEME-GC-FID and DLLME-GC-FID were 0.05 and 0.11 ng mL(-1), respectively. The relative standard deviations (RSDs, n=6) for the measurement 10 ng mL(-1) of Se(IV) were 5.32% and 4.57% with the enrichment factors of 2491 and 1129 for USAEME-GC-FID and DLLME-GC-FID, respectively. Both methods were successfully applied to the analysis of inorganic selenium in different environmental water samples and certified reference material (NIST SRM 1643e).