Multi-Residue Analysis of Some Polar Pesticides in Water Samples with SPE and LC–MS–MS

In the present study a multi-residue analytical method was developed for monitoring some polar pesticides such as acephate, methamidophos, carbofuran, isoproturon, dimethoate in water with SPE (solid-phase extraction) and LC–MS–MS. Acetochlor was taken as surrogate, and alachlor as internal standard. SPE with different types of columns was compared with LLE (liquid-liquid extraction). Further, the breakthrough volume for different pesticides was determined. The results showed that the selected pesticides can be determined very sensitively with LC–MS–MS. The minimum detectable quantity (MDQ) for each pesticide was about 1.0 ng. To date, SPE cartridge studies showed that the Oasis HLB cartridges were suitable for further studies. However, for Oasis HLB cartridge, different pesticide showed different breakthrough volume. The results showed that for acephate and methamidophos, the breakthrough volume was about 30 mL of water sample, much less than the breakthrough volume of other pesticides studied. Because of the higher vapor pressure and higher Henry's constant of methamidophos, dimethoate and carbofuran, much attention should be paid on their losses in the evaporation step of the experiment. This analytical method can be applied to determine pesticide contamination in environmental water samples. Revised: 12 September 2005 and 21 October 2005     

Comparison of different sample pre‐treatments for multi‐residue analysis of organochlorine and pyrethroid pesticides in chrysanthemum by gas chromatography with electron capture detection

The widespread use of insecticides in Chinese herbal medicines has created a compelling need for the development of a multiresidue analytical method to help assure herbs safety. The operating variables affecting the performance of the multiresidue analysis of 34 organochlorine and 12 pyrethroid pesticides in chrysanthemum, a widely used kind of Chinese herbal medicines, were evaluated. Three different extraction solvents including n‐hexane and its mixtures with acetone and petroleum ether were compared, and n‐hexane was found to be an appropriate option. A combination of gel permeation chromatography and SPE was selected as the optimum cleanup, in comparison with dispersive SPE, or the two former methods alone. The determination of the 46 pesticide residues in the spiked chrysanthemum samples was performed by GC with electron capture detection. The average recoveries ranged from 71.3 to 102.6% with RSDs of 1.4–15.7% for all of the pesticides. The LOQs were in the range of 0.0015–0.2 mg/kg, while the LODs were between 0.0005 and 0.1 mg/kg. The satisfactory accuracy, and precision, in combination with a good separation and few interferences, have demonstrated the strong potential of this technique for its application in chrysanthemum analysis.     

基于八面体理论的岩石循环加-卸载本构模型及修正

探究岩石的受力特点及破坏特性是研究岩石地下工程安全性的关键,诸多学者都期望能在岩石本构模型的研究上取得突破性进展。在此背景下,提出了一种能够描述循环加-卸载条件下岩石的本构模型。首先,假设岩石的微元强度服从八面体剪应力理论并且微元破坏服从Weibull概率公式,将岩石本构中的损伤变量以及岩石微元强度表达式里包含的损伤因子进行本构变换,得到关于应力、应变等其他表现加-卸载下岩石损伤本构模型的参数,表示出岩石微元强度和损伤变量,再将得到的岩石微元强度和损伤变量代入所提出的岩石本构模型中,并进行等式变换得到一个函数表达式。通过将其与实验数据进行拟合对比分析,得出修正后的拟合参数,将其代入函数式中,得到损伤本构模型的修正式。最后将拟合参数进行必要的敏感性分析,得出各拟合参数的实际物理意义。     

Ionic‐liquid‐based,manual‐shaking‐ and ultrasound‐assisted,surfactant‐enhanced emulsification microextraction for the determination of three fungicide residues in juice samples

A novel manual‐shaking‐ and ultrasound‐assisted surfactant‐enhanced emulsification microextraction method was developed for the determination of three fungicides in juice samples. In this method, the ionic liquid, 1‐ethyl‐3‐methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, instead of a volatile organic solvent was used as the extraction solvent. The surfactant, NP‐10, was used as an emulsifier to enhance the dispersion of the water‐immiscible ionic liquid into an aqueous phase, which accelerated the mass transfer of the analytes. Organic dispersive solvent typically required in common dispersive liquid–liquid microextraction methods was not necessary. In addition, manual shaking for 15 s before ultrasound to preliminarily mix the extraction solvent and the aqueous sample could greatly shorten the time for dispersing the ionic liquid into aqueous solution by ultrasound irradiation. Several experimental parameters affecting the extraction efficiency, including type and volume of extraction solvent, type and concentration of surfactant, extraction time, and pH, were optimized. Under the optimized conditions, good linearity with the correlation coefficients (γ) higher than 0.9986 and high sensitivity with the limit of detection ranging from 0.4 to 1.6 μg/L were obtained. The average recoveries ranged from 61.4 to 86.0% for spiked juice, with relative standard deviations from 1.8 to 9.7%. The proposed method was demonstrated to be a simple, fast, and efficient method for the analysis of the target fungicides in juice samples.     

Application of ultrasound-assisted ionic liquid dispersive liquid-phase microextraction followed high-performance liquid chromatography for the determination of fungicides in red wine

A new method was developed for the determination of fungicides in red wine using ultrasound-assisted ionic liquid dispersive liquid–phase microextraction followed by high-performance liquid chromatography. The ionic liquid, 1-hexyl-3-methylimidazolium hexafluorophosphate (IL) was quickly disrupted by ultrasonication and dispersed in wine as fine droplets. At this stage, the analytes were extracted into the fine droplets of IL. After centrifugation, the concentration of the enriched fungicides in the sedimented phase was determined. Extraction conditions including the type of extraction solvent, the extraction solvent volume, ultrasonication time, centrifugation time and sample pH were optimized. The performance of the method was studied in terms of linearity, precision, and recovery. Quantitative recoveries (>70%) except for pyrimethanil were obtained, and method precision was also satisfactory (RSD?<?10%). Enrichment factors range from 100 to 200, and the limits of detection are at the low μg per liter level for most of the target compounds.

Multi-residue determination of plant growth regulators in apples and tomatoes by liquid chromatography/tandem mass spectrometry

A sensitive and rapid multi-residue analytical method for plant growth regulators (PGRs) (i.e., chlormequat, mepiquat, paclobutrazol, uniconazole, ethephon and flumetralin) in apples and tomatoes was developed using high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). A homogenised sample was extracted with a mixture of methanol/water (90:10, v/v) and adjusted to pH <3 with formic acid. Primary secondary amine (PSA) adsorbent was used to clean up the sample. The determination was performed using electrospray ionisation (ESI) and a triple quadrupole (QqQ) analyser. Under the optimised method, the results showed that, except for ethephon, the recoveries were 81.8-98.1% in apples and tomatoes at the spiked concentrations of 0.005 to 2 mg/kg, with relative standard deviations (RSDs) of less than 11.7%. The limits of quantification (LOQs) were lower than their maximum residue limits (MRLs). The procedure was concluded as a practical method to determine the PGR residues in fruit and vegetables and is also suitable for the simultaneous analysis of the amounts of samples for routine monitoring. The analytical method described herein demonstrates a strong potential for its application in the field of PGR multi-residue analysis to help assure food safety.     

Multiresidue analytical method of pesticides in peanut oil using low-temperature cleanup and dispersive solid phase extraction by GC-MS

A method for the determination of 33 pesticides in peanut oil by GC-MS was described. Two extraction procedures based on (i) low-temperature extraction and (ii) liquid-liquid extraction were tested for the optimization of the method. The mixture of anhydrous MgSO(4) with primary secondary amine (PSA) or with PSA and C(18) was performed as sorbents in dispersive SPE. Low temperature along with PSA and C(18) cleanup gave the best results. Pesticides were identified and quantified by GC-MS in SIM mode. The correlation coefficients, R(2), in the linear range tests were better than 0.990. The average recoveries for most pesticides (spiked at 0.02, 0.05, 0.2, and 1 mg/kg) ranged from 70 to 110%, the RSD was below 20% in most instances, and LODs varied from 0.5 to 8 mug/kg.     

Determination of organophosphorus pesticides in Lycium barbarum by gas chromatography with flame photometric detection

An analytical method was developed to determine 14 organophosphorus pesticide residues in Lycium barbarum, which is both a botanical medicine and a food. A 5 g sample is mixed with 10 mL ethyl acetate and, after shaking and centrifuging, 5 mL of the upper layer is removed, concentrated, and analyzed by gas chromatography (GC) with flame photometric detection. The essential feature of this method is that, for the purpose of reducing the burden of the GC system, 0.01 g activated carbon is used to absorb pigments during the cleanup procedure. Average recoveries of 14 organophosphorus pesticides added at 0.05, 0.1, and 0.5 mg/kg were 66.84-102.42, 71.07-97.93, and 62.50-96.24%, respectively. Limits of detection ranged from 5 to 15 microg/kg. The identities of the 14 pesticides were confirmed by GC/mass spectrometry detection in the selected-ion monitoring mode. This method is sensitive, simple, rapid, inexpensive, and safe.     

Determination of Organophosphorus Pesticides in Leeks (Allium porrum L.) by GC-FPD

A method was validated for the analysis of organophosphorus pesticides in leeks. The leek sample was cut into about 2 cm lengths and heated in a microwave oven for 50 s to inactivate enzymes. The sample was extracted with 50 mL acetonitrile using an Ultra-turrax T18 blender and cleaned up by solid phase extraction. The target analytes were determined by GC with a flame photometric detector. Average recoveries were 73–118% and limits of detection ranged from 1.1 to 10.0 μg kg^?1. The uncertainty of the analysis for each pesticide was evaluated as below 16%. The method was applied to determine organophosphorus pesticides in real samples. The GC–MS was used as confirmatory tool for positive samples.     

Determination of strobilurin fungicides in cotton seed by combination of acetonitrile extraction and dispersive liquid−liquid microextraction coupled with gas chromatography

The simultaneous determination of four strobilurin fungicides (picoxystrobin, kresoxim‐methyl, trifloxystrobin, and azoxystrobin) in cotton seed by combining acetonitrile extraction and dispersive liquid?liquid microextraction was developed prior to GC with electron capture detection. Several factors, including the type and volume of the extraction and dispersive solvents, extraction condition and time, and salt addition, were optimized. The analytes were extracted with acetonitrile from cotton seed and the clean‐up was carried out by primary secondary amine. Afterwards, 60 μL of n‐hexane/toluene (1:1, v/v) with a lower density than water was mixed with 1 mL of the acetonitrile extract, then the mixture was injected into 7 mL of distilled water. A 0.1 mL pipette was used to collect a few microliters of n‐hexane/toluene from the top of the aqueous solution. The enrichment factors of the analytes ranged from 36 to 67. The LODs were in the range of 0.1 × 10^?3?2 × 10^?3 mg/kg. The relative recoveries varied from 87.7 to 95.2% with RSDs of 4.1?8.5% for the four fungicides. The good performance of the method, compared with the conventional pretreatments, has demonstrated it is suitable for determining low concentrations of strobilurin fungicide residues in cotton seed.