关键词: QuEChERS, 气相色谱-四极杆/飞行时间质谱, 农药残留, 数据库, 辣椒, 筛查确证

Abstract:

QuEChERS pretreatment combined with gas chromatography-quadrupole time-of-flight mass spectrometry (GC-Q-TOF/MS) has been investigated for application in screening 244 pesticide residues in chilli. Fresh chilli samples were extracted with acetonitrile, and dried chilli samples were extracted using an acetonitrile/acetic acid (99∶1, v/v) mixture. The two extraction solvents were stored at -20 ℃. After salting out and cleaning by dispersive solid phase extraction (dSPE), heptachlor epoxide B was added as an internal standard, and the resulting residues were dissolved in 1.00 mL acetone. The dissolved sample solution was loaded onto an HP-5MS UI column (30 m×0.25 mm, 0.25 μm) and eluted by GC-Q-TOF/MS with a programmable temperature vaporizer and splitless injection in the full-scan mode. The compensation effects of the analytical protectant (AP) and matrix-matched calibration method on the matrix effect were established. AP could be used in the fresh chilli matrix to compensate for matrix effects, but it was not effective in the dried chilli matrix. The matrix-matched calibration method was effective in both matrices, which was selected for the quantification of pesticide residues in the samples. Because of the existence of the isomers of one compound and the same characteristic ions of different compounds, analyte detection was based on a flexible retention time deviation of ±0.25 min and accurate mass deviation of ±20×10^-6. Screening was performed by the software in the automatic matching mode. Compound identification and quantitation were based on a database and calibration curve established with reference materials. Suspicious samples were subjected to manual analysis. Quantitative analysis of 244 pesticide residues in fresh chilli and 222 pesticide residues in dried chilli was performed. The results showed that the developed database and method can provide a reference for the high-throughput screening and quantitation of fresh and dried chilli. Different levels of pesticides were added to the blank chilli samples, and the addition level corresponding to a signal-to-noise ratio (S/N) of 10 was used as the limit of quantification (LOQ). The LOQs of 44 pesticides with a maximum residue limit (MRL) ≤0.05 mg/kg in fresh chilli did not exceed 0.010 mg/kg. The linear ranges of these 44 pesticides were 0.01-1.00 mg/L. At spiked levels of the LOQ and 2.5 times the LOQ, the ratios of the 44 pesticides with recoveries of 60% to 120% were 88.64% and 100%, respectively. The LOQs of 200 pesticides with MRLs ≥0.05 mg/kg or without MRLs in fresh chilli did not exceed 0.025 mg/kg. The linear ranges of these 200 pesticides were 0.05-1.00. At spiked levels of the LOQ, twice the LOQ, and 10 times the LOQ, the ratios of the 200 pesticides with recoveries of 60% to 120% were 49.50%, 87.00%, and 89.50%, respectively. The linear correlation coefficients (r ²) of the 244 pesticides in fresh chilli were greater than 0.99. The LOQs of 222 pesticides in dried chilli were less than 0.15 mg/kg, and the linear ranges were 0.04-1.00 mg/L. The ratios of these 222 pesticides with r² greater than 0.99 was 95.46%. At spiked levels of the LOQ, twice the LOQ and 10 times the LOQ in dried chilli, the ratio of the 222 pesticides with recoveries of 60% to 120% were 72.52%, 73.42%, and 81.53%, respectively. The established screening and confirmation method was used to analyze 12 fresh chilli samples and 14 dried chilli samples. Eight pesticides were found in nine fresh chilli samples and three dried chilli samples, all of which were confirmed to be positive after manual identification. The concentrations of these pesticides were lower than the MRLs required by GB 2763-2019: National Food Safety Standard-Maximum Residue Limits for Pesticides in Food. The results demonstrate that the established method is rapid, easy to execute, efficient, and reliable. It can be used for the high-throughput screening and quantitation of pesticide residues in fresh and dried chilli.

Key words: QuEChERS, gas chromatography-quadrupole time-of-flight mass spectrometry (GC-Q-TOF/MS), pesticide residues, database, chilli, screening and confirmation