A modified quick-easy-cheap-effective-rugged-and-safe method involving carbon nano-onions-based dispersive solid-phase extraction and dispersive liquid-liquid microextraction for pesticides from grapes.

A combination of modified quick easy cheap effective rugged and safe extraction approach with carbon nano-onions-based dispersive solid-phase extraction and dispersive liquid-liquid microextraction was developed for the extraction of several pesticides (diazinon, chlorpyrifos, tebuconazole, deltamethrin, permethrin, haloxyfop-methyl, penconazole, and cyhalothrin) from grape before their analysis by gas chromatography-flame ionization detection. In the extraction approach, an aliquot of grape sample is chopped and after separating its juice, the pesticides that remained in the refuse are extracted by the quick, easy, cheap, effective, rugged, and safe extraction method. The obtained acetonitrile phase is mixed with juice and the analytes are extracted by the carbon nano-onions-based dispersive solid-phase extraction. The analytes are concentrated using the microextraction procedure to obtain high enrichment factors. The results showed low limits of detection (0.5-1.6 ng/g) and quantification (1.8-5.4 ng/g) with satisfactory linearity of the calibration curves (determination coefficient, r2 ≥ 0.994). The precision of the developed method expressed as relative standard deviations was good (≤7.2%). The method provided high enrichment factors (350-410) and extraction recoveries (70-82%). Finally, seven grape samples were analyzed successfully.

Air-assisted liquid-liquid microextraction of total 3-monochloropropane-1,2-diol from refined edible oils based on a natural deep eutectic solvent and its determination by gas chromatography-mass spectrometry.

In this paper, a fast, sensitive, and selective sample preparation procedure was presented for the determination of 3-monochloropropane-1,2-diol (3-MCPD) in refined edible oils using gas chromatography-mass spectrometry. In this method, firstly, the sample lipids and analyte fatty esters are saponified by sodium hydroxide under sonication. After that the analyte was derivatized using phenylboronic acid (as the derivatization agent) and the obtained derivative was extracted during an air-assisted liquid-liquid microextraction procedure (AALLME). Six different deep eutectic solvents (DESs) were prepared as the extraction solvents and the most effective extraction for 3-MCPD was obtained in the presence of a natural DES (NDES) consisting of choline chloride (ChCl)-acetic acid (AcOH). Important variables such as sodium hydroxide concentration and volume, sonication time, temperature, extraction solvent type and volume, and phenylboronic acid concentration and volume have been optimized. Using the optimum conditions, broad linear range (0.88-1000 ng g-1), suitable coefficient of determination (0.995), and low limits of detection (0.26 ng g-1) and quantification (0.88 ng g-1) were obtained. Relative standard deviations for intra- (n=8) and inter-day (n=6) precisions at a concentration of 5 ng g-1 were 2.6 and 3.2%, respectively. The developed method has been successfully applied to 3-MCPD determination in refined edible oil samples including sunflower, corn, and canola oils.

Application of magnetic carbon nano-onions in dispersive solid-phase extraction combined with DLLME for extraction of pesticide residues from water and vegetable samples.

A dispersive solid-phase microextraction method based on magnetic carbon nano-onions (MCNOs) was developed for the extraction and preconcentration of some pesticides from water and vegetable samples. For more cleanup and preconcentration, a dispersive liquid-liquid microextraction (DLLME) method was employed after performing the first step. In this method, firstly, MCNOs were prepared and then used for adsorption of the analytes from the sample solution. After that, the adsorbed analytes were eluted with an appropriate water-miscible organic solvent and used as a dispersive solvent in the following DLLME procedure. The extracted analytes were quantified by gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. Various factors affecting the method efficiency such as sorbent weight, salt effect, pH, temperature, and type and volume of eluent and extraction solvent were optimized. This method showed wide linear ranges with a coefficient of determination ≥ 0.994, and low limits of detection (0.001-0.005 ng mL-1) and quantification (0.003-0.019 ng mL-1) under optimal conditions. Also, a good precision (relative standard deviation ≤ 8.6%) for five replicates and a satisfactory accuracy (mean relative recoveries between 82 and 99%) were obtained. It can be considered as an efficient and environment friendly method for the extraction of analytes from vegetable and fruit juices and water samples.

Development of a method based on dispersive liquid-liquid microextraction followed by partial vaporization of the extract for ultra-preconcentration of some pesticide residues in fruit juices.

A new simple and efficient method has been developed for the ultra-preconcentration of multiclass pesticide residues including penconazole, chlorpyrifos, ametryn, clodinafop-propargyl, diniconazole, oxadiazon, and fenpropathrin from some fruit juice samples based on evaporation of the sedimented organic phase obtained from dispersive liquid-liquid microextraction. The enriched target analytes were analyzed by gas chromatography-flame ionization detection. In the microextraction procedure, a mixture of iso-propanol as a disperser and 1,2-dibromoethane as an extraction solvent is quickly injected into an aqueous phase containing the analytes and centrifuged. Afterward, the sedimented phase is transferred into a special shaped vaporization vessel and vaporized with nitrogen gas stream until remaining about 2 µL of it. Eventually, 1 µL of the remained sedimented phase is removed and analyzed by separation system. The optimum extraction and disperser solvents were found to be 1,2-dibromoethane and iso-propanol, respectively. In addition, the optimum pH range was 6-8, and nitrogen gas stream at a flow rate of 90 mL min-1 in a downward oriented vessel was applied. Eventually, the limits of detection and quantification were obtained in the ranges of 45-78 and 149-261 ng L-1, respectively. Relative standard deviations at the concentrations of 300, 500 and 1000 ng L-1 of each analyte were ranged between 2.2% and 5.8% for intra-day (n = 6) precision. Inter-day (n = 3) precision at a concentration of 500 ng L-1 of each analyte was obtained in the range of 4.9-7.1%. In addition, enrichment factors and extraction recoveries were ranged from 1382-2246 and 55-89%, respectively. Finally, the method was successfully utilized in analysis of the target pesticides in the selected juices.

Combination of dispersive solid phase extraction with solidification organic drop-dispersive liquid-liquid microextraction based on deep eutectic solvent for extraction of organophosphorous pesticides from edible oil samples.

A dispersive solid phase extraction method was combined with deep eutectic solvent-based solidification of floating organic drop-dispersive liquid-liquid microextraction and used for the extraction/preconcentration of some organophosphorus pesticides residues from edible oil samples. The extracted analytes were quantified with gas chromatography-nitrogen phosphorous detector. In this procedure, the sample lipids are saponified with a sodium hydroxide solution and then the analytes are adsorbed onto a primary secondary amine sorbent. After that the analytes are desorbed with acetone as an elution/dispersive solvent and mixed with choline chloride: 3,3-dimethyl butyric acid deep eutectic solvent and the mixture is rapidly dispersed into deionized water. Then, the obtained cloudy solution is centrifuged and placed into an ice bath. The extraction solvent is solidified on the top of the solution. Finally, it is removed and dissolved in acetonitrile, and 1 µL of the solution is injected into the separation system. Validation of the method showed that limits of detection and quantification were in the ranges of 0.06-0.24 and 0.20-0.56 ng mL-1, respectively. Enrichment factors and extraction recoveries of the analytes ranged from 170-192 and 68-77%, respectively. The method had an acceptable precision with relative standard deviations less than ≤9.2% for intra- (n=6) and inter-day (n=6) precisions at four concentrations (3, 10, 50, and 250 ng mL-1, each analyte). Finally the method was used for determination of the analytes in five edible oil samples.

Preparation of a new three-component deep eutectic solvent and its use as an extraction solvent in dispersive liquid-liquid microextraction of pesticides in green tea and herbal distillates.

BACKGROUND: A new solvent, deep eutectic solvent, in which there is growing interest, has been prepared and used as an extraction solvent in the dispersive liquid-liquid method of microextraction. To prepare the solvent, dichloroacetic acid, l-menthol, and n-butanol are mixed at a molar ratio of 4:1:1 and the deep eutectic solvent is formed after heating. Then a dispersive liquid-liquid microextraction method using the prepared solvent is used for the extraction and preconcentration of some pesticides from an aqueous sample. To carry out the procedure, the deep eutectic solvent is mixed with methanol and rapidly injected by a syringe into the aqueous sample containing the analytes. After centrifuging, an aliquot of the sedimented phase is injected into the gas chromatograph. The influence of several variables on the extraction efficiency was investigated and optimized. RESULTS: Extraction recoveries and enrichment factors were obtained in the ranges of 53-86% and 1760-2853, respectively. The intra- (n = 6) and inter-day (n = 5) precision of the method was satisfactory, with relative standard deviations ≤ 7% obtained at two concentrations of 10 and 50 µg L-1 of each analyte. Moreover, detection and quantification limits for the target analytes were obtained in the ranges of 0.11-0.23 and 0.38-0.74 µg L-1 , respectively. CONCLUSION: Different samples, including green tea, rose water, lemon balm, mint, and pussy willow distillates were analyzed successfully using the method that was developed, and chlorpyrifos was found in rose water at a concentration of 17 ± 1 µg L-1 (n = 3). © 2019 Society of Chemical Industry.

Deep eutectic solvent based homogeneous liquid-liquid extraction coupled with in-syringe dispersive liquid-liquid microextraction performed in narrow tube; application in extraction and preconcentration of some herbicides from tea.

A homogeneous liquid-liquid extraction performed in narrow tube coupled to in-syringe-dispersive liquid-liquid microextraction based on deep eutectic solvent has been developed for the extraction of six herbicides from tea samples. In this method, sodium chloride as a separation agent is filled into the narrow tube and the tea sample is placed on top of the salt. Then a mixture of deionized water and deep eutectic solvent (water miscible) is passed through the tube. In this procedure, the deep eutectic solvent is realized as tiny droplets in contact with salt. By passing the droplets from the tea layer placed on the salt layer, the analytes are extracted into them. After collecting the solvent as separated layer, it is mixed with another deep eutectic solvent (choline chloride/butyric acid) and the mixture is dispersed into deionized water placed in a syringe. After adding acetonitrile to break up the cloudy state, the collected organic phase is injected into gas chromatography-mass spectrometry. Under optimal conditions, limits of detection and quantification in the ranges of 2.6-8.4 and 9.7-29 ng/kg, respectively, were obtained. The extraction recoveries and enrichment factors in the ranges of 70-89% and 350-445 were obtained, respectively.

Polyol-enhanced dispersive liquid-liquid microextraction coupled with gas chromatography and nitrogen phosphorous detection for the determination of organophosphorus pesticides from aqueous samples, fruit juices, and vegetables.

Polyol-enhanced dispersive liquid-liquid microextraction has been proposed for the extraction and preconcentration of some organophosphorus pesticides from different samples. In the present study, a high volume of an aqueous phase containing a polyol (sorbitol) is prepared and then a disperser solvent along with an extraction solvent is rapidly injected into it. Sorbitol showed the best results and it was more effective on the extraction recoveries of the analytes than inorganic salts such as sodium chloride, potassium chloride, and sodium sulfate. Under the optimum extraction conditions, the method showed low limits of detection and quantification within the ranges of 12-56 and 44-162 pg/mL, respectively. Enrichment factors and extraction recoveries were in the ranges of 2799-3033 and 84-92%, respectively. The method precision was evaluated at a concentration of 10 ng/mL of each analyte, and relative standard deviations were found to be less than 5.9% for intraday (n = 6) and less than 7.8% for interday (n = 4). Finally, some aqueous samples were successfully analyzed using the proposed method and four analytes (diazinon, dimethoate, chlorpyrifos, and phosalone) were determined, some of them at ng/mL level.

A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air-assisted liquid-liquid microextraction from human urine and plasma samples followed by gas chromatography-nitrogen phosphorous detection.

In present study, a simultaneous derivatization and air-assisted liquid-liquid microextraction method combined with gas chromatography-nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1-flouro-2,4-dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05-0.34 ng mL(-1) are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples.

Gas chromatographic determination of some phenolic compounds in fuels and engine oil after simultaneous derivatization and microextraction.

In this study, a simultaneous derivatization/air-assisted liquid-liquid microextraction method has been developed for sample preparation of some phenolic compounds in fuels and engine oil. Analytes are transferred by back liquid-liquid extraction into NaOH solution and then are derivatized with butyl chloroformate and extracted simultaneously into carbon tetrachloride. The extracted derivatized analytes are analyzed using gas chromatography with flame ionization detection. The effect of extracting solvent type, derivatization agent and extraction solvent volumes, ionic strength of the aqueous solution, number of extraction cycles, etc., on the extraction efficiency is investigated. The calibration graphs are linear in the range of 3-10,000 µg/L. Enhancement factors, enrichment factors, and extraction recoveries are in the ranges of 497 to 1471, 571 to 991, and 60 to 109%, respectively. Detection limits are obtained in the range of 0.8 to 2.0 µg/L. Relative standard deviations for the extraction of each selected phenols are in the ranges of 2-4% for intraday (n = 6) and 3-6% (n = 5) for interday precisions for 200 µg/L. This technique is successfully applied for the extraction, preconcentration, and determination of the selected phenols in gasoline, kerosene, gas oil, and engine oil.

Development of a new microextraction method based on elevated temperature dispersive liquid-liquid microextraction for determination of triazole pesticides residues in honey by gas chromatography-nitrogen phosphorus detection.

In the present study, a rapid, highly efficient, and reliable sample preparation method named "elevated temperature dispersive liquid-liquid microextraction" followed by gas chromatography-nitrogen-phosphorus detection was developed for the extraction, preconcentration, and determination of five triazole pesticides (penconazole, hexaconazole, diniconazole, tebuconazole, and difenoconazole) in honey samples. In this method the temperature of high-volume aqueous phase was adjusted at an elevated temperature and then a disperser solvent containing an extraction solvent was rapidly injected into the aqueous phase. After cooling to room temperature, the phase separation was accelerated by centrifugation. Various parameters affecting the extraction efficiency such as type and volume of the extraction and disperser solvents, temperature, salt addition, and pH were evaluated. Under the optimum extraction conditions, the method resulted in low limits of detection and quantification within the range 0.05-0.21ngg(-1) in honey (15-70ngL(-1) in solution) and 0.15-1.1ngg(-1) in honey (45-210ngL(-1) in solution), respectively. Enrichment factors and extraction recoveries were in the ranges of 1943-1994 and 97-100%, respectively. The method precision was evaluated at 1.5ngg(-1) of each analyte, and the relative standard deviations were found to be less than 4% for intra-day (n=6) and less than 6% for inter-days. The method was successfully applied to the analysis of honey samples and difenoconazole was determined at ngg(-1) levels.