High-throughput multipesticides residue analysis in earthworms by the improvement of purification method: Development and application of magnetic Fe3 O4 -SiO2 nanoparticles based dispersive solid-phase extraction.

As a key representative organism, earthworms can directly illustrate the influence of pesticides on environmental organisms in soil ecosystems. The present work aimed to develop a high-throughput multipesticides residue analytical method for earthworms using solid-liquid extraction with acetonitrile as the solvent and magnetic material-based dispersive solid-phase extraction for purification. Magnetic Fe3 O4 nanoparticles were modified with a thin silica layer to form Fe3 O4 -SiO2 nanoparticles, which were fully characterized by field-emission scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffractometry, and vibrating sample magnetometry. The Fe3 O4 -SiO2 nanoparticles were used as the separation media in dispersive solid-phase extraction with primary secondary amine and ZrO2 as the cleanup adsorbents to eliminate matrix interferences. The amounts of nanoparticles and adsorbents were optimized for the simultaneous determination of 44 pesticides and six metabolites in earthworms by liquid chromatography with tandem mass spectrometry. The method performance was systematically validated with satisfactory results. The limits of quantification were 20 µg/kg for all analytes studied, while the recoveries of the target analytes ranged from 65.1 to 127% with relative standard deviation values lower than 15.0%. The developed method was subsequently utilized to explore the bioaccumulation of bitertanol in earthworms exposed to contaminated soil, verifying its feasibility for real sample analysis.

Simultaneous determination of 114 pesticides in complex Chinese herbal medicine Fritillaria using ordered mesoporous carbon CMK-3 as a reversed-dispersive solid phase extraction sorbent.

Fritillaria, a traditional Chinese herbal medicine, is classified into many medicinal species and contains numerous complex components. It is thus difficult to simultaneously detect multiple pesticide residues in different Fritillaria species. An easy, reliable, and widely applicable analytical method based on a modified Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method coupled with LC-MS/MS was developed to solve these problems encountered during pesticide residue analysis in complex Fritillaria matrices. Ordered mesoporous carbon CMK-3 and a primary secondary amine (PSA) were used as efficient purification sorbents by optimization of the QuEChERS process. Systematic method validation was performed for four species of Fritillaria. The matrix effect of pesticides varied among different Fritillaria species, and matrix-matched standard solutions were thus employed for quantitative analysis. The mean recoveries of all pesticides ranged from 88.6% to 95.5%, with mean relative standard deviations (RSD) lower than 6% at spiked concentrations of 30, 120, and 240 µg kg-1. The limits of quantification (LOQ) for the developed method were in the range of 30-120 µg kg-1. This method was further used to analyze 47 Fritillaria samples from Zhejiang province, China, and seven pesticides were detected in 22 Fritillaria samples. These results demonstrate that the developed method is suitable for an accurate analysis of multiple pesticide residues in various Fritillaria.

Removal of Matrix Interferences by Nano-MgO and Co-Adsorbents for Accurate Multi-Pesticide Residue Analysis in the Chinese Medicinal Herb, Paeoniae Radix Alba.

A simple, accurate, and high-throughput analytical method was developed to detect 123 pesticide residues in Chinese medicinal herb Paeoniae Radix Alba (PRA) by introducing nano-MgO as a highly efficient purification material based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) design concept. Various PRA samples were extracted using 8 mL 0.5% acetic acid-acetonitrile solution and purified by a dispersive solid-phase extraction method with 30 mg nano-MgO, 40 mg primary secondary amine (PSA), and 40 mg octadecylsilane (C18) as the cleanup adsorbents, followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS). 70.7% of pesticides showed a weak matrix effect after the purification process, indicating that this method can give the precise quantitative analysis of trace pesticides residue. The method was systematically validated under optimal conditions in five different kinds of PRA samples; good linearity was observed in the concentration range of 0.5-250 µg/L or 1-250 µg/L. Pesticide recovery in each sample spiked at concentrations of 20, 50, and 200 µg/kg ranged from 98.0% to 111% and the mean relative standard deviation ranged from 2.72% to 5.70%. Furthermore, the method comparison with the traditional QuEChERS method suggested the feasibility, advantages, and potential application prospect of the present method for the multi-pesticide residue analysis in various PRA samples.

Magnetic covalent organic framework as a solid-phase extraction absorbent for sensitive determination of trace organophosphorus pesticides in fatty milk.

A simple and efficient magnetic solid-phase extraction (MSPE) method was established with magnetic covalent organic framework (COF) as adsorbent to enrich organophosphorus pesticides from fatty milk samples, followed by the sensitive determination via LC-MS/MS. The key parameters influencing the MSPE efficiency were comprehensively investigated to afford an optimized procedure. All the target analytes could be captured directly by magnetic COF from milk without protein precipitation, making the pretreatment rapid and convenient. Systematic method validation demonstrated its satisfactory linearity, recoveries (80.0-105 %), and precision (RSDs <12.3 %). The method limits of quantification were 0.2-0.5 µg L-1. A comparison experiment to the reported solid-phase extraction fully verified the present MSPE more rapid, accurate, and environment-friendly. Furthermore, FT-IR and XPS analysis were performed to reveal the adsorption mechanisms of magnetic COF to organophosphorus pesticides, which could offer guidance on the rational design of COF adsorbent for various target analytes.

Significant role of supercritical fluid chromatography - mass spectrometry in improving the matrix effect and analytical efficiency during multi-pesticides residue analysis of complex chrysanthemum samples.

As an important "food and drug dual-use" product, chrysanthemums are widely used in both botanical medicine and food applications. However, the misuse of pesticides during chrysanthemum cultivation makes pesticide residue monitoring crucial. The aim of the present work was to address this practical demand for the simultaneous determination of multiple pesticide residues in various species of chrysanthemums. Both the sample pre-treatment and instrumental methods were systematically investigated. Seven chrysanthemum samples were extracted using acetonitrile and purified by dispersive solid-phase extraction with amino-modified multi-walled carbon nanotubes (MWCNTs-NH2) and C18 as the cleanup co-adsorbents. After optimizing the amounts of MWCNTs-NH2 and C18, matrix effects could not be avoided during LC-MS/MS analysis of 112 pesticides, although satisfactory recoveries were obtained. The use of SFC-MS/MS was evaluated, which demonstrated the significant positive role of SFC-MS/MS in reducing the matrix effects during pesticide residue analysis. In addition, the use of SFC-MS/MS permitted a shorter run time and afforded greater analytical efficiency. Method validation was further performed to evaluate the linearity, sensitivity, recovery, and precision of the developed method. Good linearity was observed for 92% of the analytes in the concentration range of 2-250 µg L-1 for all seven of the chrysanthemum samples. The LODs of the 112 pesticides ranged from 0.01 to 31.41 µg L-1, depending on the sample, while the mean recoveries of all of the spiked pesticides ranged from 81.8% to 102% for concentrations of 20, 50, and 200 µg kg-1. These results clearly demonstrate the applicability of the developed method for the simultaneous determination of multi-pesticides in various chrysanthemum samples.

Enantioselective analysis and degradation of isofenphos-methyl in vegetables by liquid chromatography-tandem mass spectrometry.

The enantioselective degradation of isofenphos-methyl in cowpea, cucumber, and pepper under field conditions was investigated to elucidate the enantioselective environmental behaviors of this pesticide. The concentrations of the enantiomers were determined by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The degradation rates of isofenphos-methyl enantiomers were the fastest in cowpea, followed by cucumber and pepper, with half-lives ranging from 1.48 to 8.06 days. The enantioselective degradation of isofenphos-methyl was characterized by calculating and comparing the values of enantiomer fraction (EF) and enantiomeric selectivity (ES). The degradation rates and enantioselectivities of isofenphos-methyl were different for the three vegetables. (R)-(-)-isofenphos-methyl was degraded faster than (S)-(+)-isofenphos-methyl in cowpea and cucumber, whereas (S)-(+)-isofenphos-methyl underwent preferential degradation in pepper. These results could serve as a reference for the study of enantioselective behavior of isofenphos-methyl in plants and further food safety evaluation, where the enantiomeric differences should be considered in the risk assessment.

Stereoselective Analysis and Degradation of Pyrisoxazole in Cabbage, Pakchoi, and Pepper by Liquid Chromatography Tandem Mass Spectrometry.

Pyrisoxazole is a chiral fungicide with high sterilizing activity to the plant pathogenic bacteria and thus can be used for protecting the vegetables from gray mold, powdery mildew, and brown rot. The present work aimed to explore its stereoselective degradation in cabbage, pakchoi, and pepper samples. The enantioseparation and analysis on chiral column Lux Cellulose-3 based on liquid chromatography tandem mass spectrometry was developed coupled to the QuEChERS method. The recoveries of the stereoisomers in various vegetables ranged from 72.6 to 124% with RSD lower than 5.0%. Enantioselective dissipation of pyrisoxazole in vegetables displayed that (-)-A-pyrisoxazole was preferentially degraded versus (+)-A-pyrisoxazole in all the vegetables. (+)-B-pyrisoxazole was preferentially degraded in cabbage, while there was no obvious enantioselectivity in pakchoi and pepper. Meanwhile, stereoselectivity analysis demonstrated that (±)-A-pyrisoxazole was degraded faster than (±)-B-pyrisoxazole in pakchoi and pepper, while there was no stereoselective degradation in cabbages.