Simultaneous Determination of 26 Pesticide Residues in Traditional Chinese Medicinal Leeches by Modified QuEChERS Coupled with HPLC-MS/MS.

A Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) pretreatment technique combined with HPLC-MS/MS was established to detect 26 pesticides in traditional Chinese medicinal leeches. The sample was extracted by acetonitrile solution with sodium acetate-0.1% (v/v) acetic acid as a buffer system, then cleaned up by a mixture of 750 mg of MgSO4, 150 mg of C18, and 150 mg of PSA, separated by an ACQUITY BEH C18 column, and determined in the dynamic multiple reaction mode. Under the optimized conditions, the peak areas of the 26 pesticides in leeches showed good linearity (r > 0.99) between their mass concentrations from 1 to 100 µg/L. At the spike levels of 10, 20, and 100 µg/kg, the recoveries of 26 pesticides in leeches were 72.9-101.6% with an RSD of 1.1-12.8%, an LOQ of 10 µg/kg, and an LOD of 0.1-5.4 µg/kg. This method is easy, rapid, sensitive, and practical and meets the requirements of pesticide residue detection standards.

Simultaneous detection of four pesticides in agricultural products by a modified QuEChERS method and LC-MS/MS.

A modified QuEChERS pretreatment method and LC-MS/MS technique were performed to simultaneously determine four pesticide (Hexachlorophene, Dinex, Dinosam, Dinoterb) residues in agricultural products. Through the optimization of LC-MS/MS detection parameters in SIM mode, the optimal instrument conditions are obtained. The modified QuEChERS method was used to pretreat the samples. Solid phase extractants PSA, C18 and GCB were used for sample purification. The research results showed that the correlation coefficients of the four pesticides were all greater than 0.991, which had a good linear relationship. The limits of quantitation (LOQ) of the four pesticides were 0.05-0.56 µg/kg. The recoveries were 70.51-113.20% with relative standard deviations (RSDS) of 1.6-11.2%. The developed method can provide reliable data support for the subsequent simultaneous detection of these four pesticides.

Investigation and Analysis of Pesticide Residues in Four Common Vegetables and Risk Assessment of Dietary Exposure in Ceramic Capital, China.

In order to understand the basic situation of pesticide residues in vegetables in China's porcelain capital, four kinds of common vegetables on the market were selected in this study for detection and analysis of pesticide residues. The pesticide residues in vegetables were analyzed through sample selection, optimization of instrument and equipment conditions, and comparison of detection pass rates. The sampling locations were common vegetables purchasing places such as large and medium-sized supermarkets. QuEChERS method was used as the sample pretreatment, and gas chromatography (GC-MS/MS) was used for quantitative analysis. Finally, the exposure risk of pesticides was assessed according to the test results. The results showed that all the pesticides were detected in four kinds of vegetables, but the detected pesticides did not exceed the national standard (GB 2763-2014, China). Moreover, the target risk coefficient (THQ) and risk index (HI) values of four vegetables were less than one, indicating that the combined and toxic effect of pesticide residual mixed contamination was smaller in four vegetables. Therefore, there was no significant harm from people using these vegetables.

Degradation of a Novel Pesticide Antiviral Agent Vanisulfane in Aqueous Solution: Kinetics, Identification of Photolysis Products, and Pathway.

Hydrolysis degradation kinetics of vanisulfane in water was investigated in detail under exogenous substances conditions. The experimental results indicated that the degradation rate of vanisulfane in aqueous solution increases with the increase of concentration of Cu2+. The degradation of vanisulfane did not change significantly in Ni2+, Zn2+, Pb2+, and Fe3+ aqueous solutions. Surfactants have no significant effect on the degradation of vanisulfane, and the degradation rate of vanisulfane increases with increasing concentration of fulvic acid. In addition, the photolysis products were identified by ultra-high-performance liquid chromatography coupled with Orbitrap high-resolution mass spectrometry. Five photolysis products were identified, and the degradation reaction pathway and the mechanism of vanisulfane were proposed, which mainly involved cleavage of thioether, back into aldehyde, cleavage of ether bond, demethylation, and intramolecular dehydration processes. This research on vanisulfane can be helpful for its security evaluation and increased understanding of vanisulfane in water environments.

Qualitative and Quantitative Analysis of the New Sulfone Bactericide 2-(4-Fluorophenyl)-5-(Methylsulfonyl)-1,3,4-Oxadiazole and Identification of Its Degradation Pathways in Paddy Water.

Rapid and simple methods for the determination of Jiahuangxianjunzuo (JHXJZ) in paddy water, brown rice, soil and rice straw was developed and validated. This method involved the use of ultrahigh-performance liquid chromatography equipped with photodiode array detector. The most important factor was chromatographic conditions, as identified through an orthogonal experimental design. This method showed good recoveries and precisions, thereby indicating its suitability for monitoring of JHXJZ residues in paddy water, brown rice, soil and rice straw. Furthermore, hydrolysis experiment was conducted in the laboratory under pH = 7 buffer solutions, and its degradation product was identified as 2-(4-fluorophenyl)-5-methoxy-1,3,4-oxadiazole by high-resolution mass spectrometry. JHXJZ has a major degradation pathway in the water which the OH- nucleophilic attack the C5 of 1,3,4-oxadiazole ring. Then it leaves mesyl to form intermediate 5-(4-fluorophenyl)-1,3,4-oxadiazol-2-ol and the intermediate combined with methanol formed the degradation product 2-(4-fluorophenyl)-5-methoxy-1,3,4-oxadiazole by the loss of one H2O.The degradation pathways of JHXJZ under the present indoor simulation conditions were proposed.

Hydrolysis and Photolysis Kinetics, and Identification of Degradation Products of the Novel Bactericide 2-(4-Fluorobenzyl)-5-(Methylsulfonyl)-1,3,4-Oxadiazole in Water.

Hydrolysis and photolysis kinetics of Fubianezuofeng (FBEZF) in water were investigated in detail. The hydrolysis half-lives of FBEZF depending on pH, initial concentration, and temperature were (14.44 d at pH = 5; 1.60 d at pH = 7), (36.48 h at 1.0 mg L-1; 38.51 h at 5.0 mg L-1; and 31.51 h at 10.0 mg L-1), and (77.02 h at 15 °C; 38.51 h at 25 °C; 19.80 h at 35 °C; and 3.00 h at 45 °C), respectively. The photolysis half-life of FBEZF in different initial concentrations were 8.77 h at 1.0 mg L-1, 8.35 h at 5.0 mg L-1, and 8.66 h at 10.0 mg L-1, respectively. Results indicated that the degradation of FBEZF followed first-order kinetics, as the initial concentration of FBEZF only had a slight effect on the UV irradiation effects, and the increase in pH and temperature can substantially accelerate the degradation. The hydrolysis Ea of FBEZF was 49.90 kJ mol-1, which indicates that FBEZF belongs to medium hydrolysis. In addition, the degradation products were identified using ultra-high-performance liquid chromatography coupled with an Orbitrap high-resolution mass spectrometer. One degradation product was extracted and further analyzed by ¹H-NMR, 13C-NMR, 19F-NMR, and MS. The degradation product was identified as 2-(4-fluorobenazyl)-5-methoxy-1,3,4-oxadiazole, therefore a degradation mechanism of FBEZF in water was proposed. The research on FBEZF can be helpful for its safety assessment and increase the understanding of FBEZF in water environments.

Multiresidue determination of 29 pesticide residues in pepper through a modified QuEChERS method and gas chromatography-mass spectrometry.

This study describes the development and use of a modified quick, easy, cheap, effective, rugged and safe (QuEChERS) method coupled with gas chromatography with mass spectrometry to determine 29 pesticide residues in green, red and dehydrated red peppers. Pesticides were extracted with acetonitrile (1% acetic acid), partitioned with sodium chloride and purified with primary secondary amino and octadecyl silane in acetone. The QuEChERS extraction conditions were optimized, and the matrix effects that might influence recoveries were evaluated and minimized using matrix-matched calibration curves. Under the optimized conditions, the calibration curves for 29 pesticides showed good linearity in the concentration range of 0.1-10 µg/mL with determination coefficient R(2) > 0.998. The limits of quantification of the 29 pesticides were 0.006-0.06 mg/kg for green pepper, 0.005-0.039 mg/kg for red pepper and 0.014-0.25 mg/kg for dehydrated red pepper. These values are below the suggested regulatory maximum residue limits. The mean recoveries ranged between 70.1 and 110%, and the relative standard deviations were <13%. The developed method was successfully applied to commercial samples. Some samples were found to contain the 29 pesticides with levels below the legal limits. Copyright © 2016 John Wiley & Sons, Ltd.

Enantioselective degradation of indoxacarb from different commercial formulations applied to tea.

The stereoselective degradation of indoxacarb enriched with (+)-S-indoxacarb (S/R:70/30) was investigated in three typical green teas. A convenient and precise chiral method was developed and validated for measuring indoxacarb enantiomers in green tea. The developed method was based on high-performance liquid chromatography coupled with tandem mass spectrometry using a Chiralpak IC column. The stereoselective degradation of indoxacarb enantiomers showed that the (+)-S-enantiomer dissipated faster than the (-)-R-enantiomer in all three typical tea farms. However, no enantiomerization was observed after applying pure (+)-S-indoxacarb. Residues on tea plant of the active ingredient (+)-S-indoxacarb from suspension concentrate (SC) was more persistent than that from emulsifiable concentrate (EC).