Ionic Liquid-Dispersive Micro-Extraction and Detection by High Performance Liquid Chromatography-Mass Spectrometry for Antifouling Biocides in Water.

A simple analytical method was developed and evaluated for the determination of two antifouling biocides using an ionic liquid-dispersive liquid-liquid micro-extraction (IL-DLLME) and a high-performance liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) analysis. Irgarol 1051 and Sea-Nine 211 were extracted from deionized water, lake water, and seawater using IL 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIm][PF6]) and ethyl acetate as the extraction solvent and the dispersion solvent. Several factors were considered, including the type and volume of extraction and dispersive solvent, IL amount, sample pH, salt effect, and cooling temperature. The developed method resulted in a recovery range of 78.7-90.3%, with a relative standard deviation (RSD, n = 3) less than 7.5%. The analytes were enriched greater than 40-fold, and the limits of detection (LOD) for two antifouling biocides were 0.01-0.1 µg L-1. The method was effectively applied for the analysis of real samples of freshwater as well as samples of seawater.

Utilizing a Rapid Multi-Plug Filtration Cleanup Method for 72 Pesticide Residues in Grape Wines Followed by Detection with Gas Chromatography Tandem Mass Spectrometry.

A convenient and fast multi-residue method for the efficient identification and quantification of 72 pesticides belonging to different chemical classes in red and white grape wines has been developed. The analysis was based on gas chromatography tandem quadrupole mass spectrometric determination (GC-MS/MS). The optimization strategy involved the selection of the amount of multi-walled carbon nanotubes (MWCNTs) and the number of cleanup procedure cycles for multi-plug filtration cleanup (m-PFC) to achieve ideal recoveries and reduce the sample matrix compounds in the final extracts. The optimized procedure obtained consistent recoveries between 70.2 and 108.8% (70.2 and 108.8% for white wine, and 72.3 and 108.4% for red wine), with relative standard deviations (RSDs) that were generally lower than 9.2% at the three spiking levels of 0.01, 0.05 and 0.1 mg/kg. The linearity was studied in the range between 0.002 and 0.1 mg/kg using pesticide standards prepared both in pure solvent and in the presence of the matrix, showing coefficients of determination (R2) higher than 0.9495 for all the pesticides. To improve accuracy, matrix-matched calibration curves were used for calculating the quantification results. Finally, the method was used successfully for detecting pesticide residues in commercial grape wines.

Decrease of pirimiphos-methyl and deltamethrin residues in stored rice with post-harvest treatment.

A modified quick, easy, cheap, effective, rugged (QuEChERS) method with multi-walled carbon nanotubes (MWCNTs) as reversed-dispersive solid phase extraction (r-DSPE) material was applied to the analysis of pirimiphos-methyl and deltamethrin residues in stored rice. Two dustable powder (DP) formulations (2% pirimiphos-methyl and deltamethrin DP; 5% pirimiphos-methyl DP) were applied in simulated storehouse trials in the lab. The residues and dissipation of the two pesticides in stored rice were investigated. Slow dissipation of both pesticides was observed in stored rice. The half-lives of pirimiphos-methyl were 23.9-28.9 days, and those of deltamethrin were 23.9-24.8 days. Residues of pirimiphos-methyl from application rates of 4.5-6.75 a.i. mg/kg (active ingredient milligram per kilogram) and 10-15 a.i. mg/kg were 1.6-3.8 mg/kg and 3.0-4.5 mg/kg at 60 days Pre-harvest Interval (PHI). Residues of deltamethrin from an application rate of 0.5-0.75 a.i. mg/kg were 0.13-0.14 mg/kg at 60 days PHI. Both pesticides residues were below the Maximum Residue Limits (MRLs) established by the Codex Alimentarius Commission (CAC). Therefore, at the recommended dosages they are safe for use on stored rice.

Simultaneous determination of 36 pesticide residues in spinach and cauliflower by LC-MS/MS using multi-walled carbon nanotubes-based dispersive solid-phase clean-up.

A multi-residue method based on a modified QuEChERS sample preparation with multi-walled carbon nanotubes (MWCNTs) as reversed-dispersive solid-phase extraction (r-DSPE) material and LC-MS/MS determination by MRM mode was validated for 36 representative pesticides in spinach and cauliflower. It was demonstrated that MWCNTs can be used as effective r-DSPE materials with the QuEChERS method for the clean-up of extract from different matrices. However, MWCNTs could absorb pyrimethanil, diflubenzuron, and chlorbenzuron in both spinach and cauliflower, which leads to the low recoveries compared with PSA. The LODs and LOQs for 36 pesticides ranged from 0.1 to 5 µg kg(-1) and from 2 to 30 µg kg(-1), respectively. Good linearity was found for all pesticides with coefficients better than 0.995 in a range of 0.02-0.5 mg l(-1). The developed method with MWCNTs clean-up was successfully used to determine the 36 pesticides in real samples.

Influence of different planting seasons of six leaf vegetables on residues of five pesticides.

To investigate the influence of different planting seasons on the dissipation of pesticides, field experiments of thiophanate-methyl, metalaxyl, fluazifop-P-butyl, chlorpyrifos, and λ-cyhalothrin on six crops including pakchoi, rape, crown daisy, amaranth, spinach, and lettuce were designed and conducted. In this study, a high-performance liquid chromatography and electrospray ionization-tandem mass spectrometer with multiple reaction monitoring was used to simultaneously determine thiophanate-methyl and its metabolite carbendazim, metalaxyl, and fluazifop-P-butyl in various samples; gas chromatography with an electron capture detector was used to detect chlorpyrifos and λ-cyhalothrin. The limits of quantitation (LOQs) of these six pesticides were in the range of 0.001-0.01 mg kg(-1) for all samples, and the average recoveries of all pesticides ranged from 60.1 to 119.1% at 0.01 and 0.1 mg kg(-1) spiked levels. The relative standard deviation (RSD) ranged from 1.1 to 13.9%. All maximal concentrations of the six pesticides in six leaf vegetables in autumn were higher than in summer in Beijing. For most pesticides half-lives in autumn were longer than in summer. The results showed that the initial concentration, maximal concentration, and half-lives of pesticides were influenced not only by environmental factors such as light, heat, moisture, and rainy climate but also by plant matrices.

Multiplug filtration clean-up with multiwalled carbon nanotubes in the analysis of pesticide residues using LC-ESI-MS/MS.

A novel design for a rapid clean-up method was developed for the analysis of pesticide residues in fruit and vegetables followed by LC-ESI-MS/MS. The acetonitrile-based sample extraction technique was used to obtain the extracts, and further clean-up was carried out by applying the streamlined procedure on a multiplug filtration clean-up column coupled with a syringe. The sorbent used for clean-up in this research is multiwalled carbon nanotubes, which was mixed with anhydrous magnesium sulfate to remove water from the extracts. This method was validated on 40 representative pesticides and apple, cabbage, and potato sample matrices spiked at two concentration levels of 10 and 100 µg/kg. It exhibited recoveries between 71 and 117% for most pesticides with RSDs < 15%. Matrix-matched calibrations were performed with the coefficients of determination >0.995 for most studied pesticides between concentration levels of 10-500 µg/L. The LOQs for 40 pesticides ranged from 2 to 50 µg/kg. The developed method was successfully applied to the determination of pesticide residues in market fruit and vegetable samples.

Removal of aflatoxin B(1) in edible plant oils by oscillating treatment with alkaline electrolysed water.

Alkaline electrolysed water (AlEW) with different pHs was produced by an electrolysed water generator through adjusting the electric current and voltage. The produced AlEW had a pH above 10, and a low oxidation-reduction potential (ORP) of less than -560 mV. In the current study, the effectiveness of AlEW on decontamination of aflatoxin B1 (AFB1) in various edible plant oils was investigated. The character of AlEW, oil type and the volume of AlEW were major factors which could influence the AFB1 elimination effectiveness. AlEW with pH 12.2 had the greater potential to remove AFB1. When 10 ml AlEW with pH 12.2 were added to 5 g peanut oil or olive oil (fortified level at 40 µg kg(-1)), followed by oscillation for 5 min at 20 °C, the removal rate of AFB1 could reach nearly 100%. The volume of AlEW needed to completely remove the AFB1 varied with the pH of AlEW and with the oil type. The degradation products of AFB1 were also investigated.

Spinach or amaranth contains highest residue of metalaxyl, fluazifop-P-butyl, chlorpyrifos, and lambda-cyhalothrin on six leaf vegetables upon open field application.

To select representative leaf vegetables which may contain the highest residue, field experiments of metalaxyl, fluazifop-P-butyl, chlorpyrifos, and lambda-cyhalothrin on six crops including pakchoi, rape, crown daisy, amaranth, spinach, and lettuce were designed and conducted. In this study, a high-performance liquid chromatograph and electrospray ionization tandem mass spectrometer with multiple reaction monitoring was used to simultaneously determine metalaxyl and fluazifop-P-butyl residue in various samples, and a gas chromatograph with electron capture detector was used to detect chlorpyrifos and lambda-cyhalothrin. The limits of quantification (LOQ) of metalaxyl, fluazifop-P-butyl, chlorpyrifos, and lambda-cyhalothrin were in the range of 0.001-0.01 mg kg(-1) for all samples, and the average recoveries of all pesticides ranged from 67.6 to 119.1% at spiked levels of 0.01-0.1 mg kg(-1). In supervised field trials, the half-lives of metalaxyl, fluazifop-P-butyl, chlorpyrifos, and lambda-cyhalothrin were in the range of 1.11-3.79 days, 1.11-2.27 days, 1.13-5.17 days, and 1.77-6.24 days. It was also found that all pesticide residues in spinach and/or amaranth were higher than others after application. It is recommended that spinach or amaranth can be selected as a representative crop of leaf vegetables in studying systemic fungicide, insecticides, and herbicides with similarity as metalaxyl, fluazifop-P-butyl, chlorpyrifos, and lambda-cyhalothrin.

Spinach or amaranth may represent highest residue of thiophanate-methyl with open field application on six leaf vegetables.

To select representative crop among leaf vegetables which may contain the highest residue after fungicide uses, open field applications with thiophanate-methyl on six crops including pakchoi, rape, crown daisy, amaranth, spinach and lettuce were designed and conducted. In this study, a high-performance liquid chromatography and electrospray ionization-tandem mass spectrometry with selected reaction monitoring was used to simultaneously determine thiophanate methyl and its metabolite carbendazim residue in various samples. The limit of quantification for thiophanate methyl and carbendazim were established in the range of 0.005-0.01 mg kg(-1) for all samples. It was shown that recoveries ranged from 67.8 % to 102.3 % for thiophanate methyl, and 72.0 %-112.6 % for carbendazim at spiked levels of 0.01-0.1 mg kg(-1). It's found that thiophanate methyl converts to carbendazim very quickly. In supervised field trials, the half-lives of thiophanate methyl in six leaf vegetables were in the range of 1.26-2.65 days, and the half-lives of carbendazim were in the range of 2.53-4.28 days. It was also found that thiophanate methyl residue in spinach and amaranth was higher than others after application. It's recommended that spinach or amaranth can be selected as representative crop in leaf vegetables in study of systemic fungicides with similarity as thiophanate methyl.

Determination of six neonicotinoid insecticides residues in spinach, cucumber, apple and pomelo by QuEChERS method and LC-MS/MS.

A modified QuEChERS and LC-MS/MS method has been developed for the simultaneous determination of residues of six neonicotinoids in various crops, including spinach, cucumber, apple and pomelo. The method showed good linearity (R(2) ≥ 0.9995) and precision (RSD ≤ 14.0%). Average recoveries of the six neonicotinoids ranged between 73.7% and 103.8% at spiking levels 0.005, 0.1 and 1 mg kg(-1). The LODs and LOQs were in the ranges of 0.20-0.85 µg kg(-1) and 0.66-2.84 µg kg(-1), respectively. The method was satisfactorily validated for the analysis of 50 agricultural samples. Imidacloprid and imidaclothiz were detected at concentration levels ranging from 7 to 5.3 µg kg(-1).