GPC-QuEChERS-GC-MS/MS法测定胡椒油树脂、胡椒精油中4种农药残留及其膳食风险评估  

Determination of Four Pesticide Residues in Pepper Oleoresin and Pepper Essential Oil Using GPC-QuEChERS-GC-MS/MS and Dietary Risk Assessment

作　　者：钱建瑞 张玉芬 李晓伟 武亚明 张晓芳 吴迪 QIAN Jian-rui;ZHANG Yu-fen;LI Xiao-wei;WU Ya-ming;ZHANG Xiao-fang;WU Di(Chenguang Biotech Group Co.,Ltd.,Handan 057250,China;Hebei Chenguang Detection Technology Service Co.,Ltd.,Handan 057250,China;Natural Pigment Industry Research Institute of Hebei,Handan 057250,China)

机构地区：[1]晨光生物科技集团股份有限公司,河北邯郸057250 [2]河北晨光检测技术服务有限公司,河北邯郸057250 [3]河北省植物天然色素产业技术研究院,河北邯郸057250

出　　处：《质谱学报》2025年第2期233-241,I0005,共10页Journal of Chinese Mass Spectrometry Society

摘　　要：本研究建立了胡椒油树脂、胡椒精油中甲霜灵、毒死蜱、氯菊酯、氯氰菊酯4种农药残留的凝胶渗透色谱-QuEChERS-气相色谱-串联质谱(GPC-QuEChERS-GC-MS/MS)检测方法。采用乙酸乙酯-环己烷溶液(1:1,V/V)提取,使用凝胶色谱仪结合石墨化碳黑吸附剂(GCB)、N-丙基乙二胺固相吸附剂(PSA)进行净化,多反应监测(MRM)模式检测,基质匹配标准曲线内标法定量分析。在优化的条件下,4种农药在3~100μg/L浓度范围内的线性关系良好,相关系数均大于0.99,方法检出限为0.04~0.10 mg/kg,3个不同加标水平下的回收率均在73%~120%之间,相对标准偏差(RSD)均小于20%。收集市场上的胡椒、胡椒精油、胡椒油树脂各20批次,采用本方法检测样品中甲霜灵、毒死蜱、氯菊酯、氯氰菊酯的最高残留量分别为1.236、0.954、2.087、1.174 mg/kg。基于实际样品中农药残留中位值,评估了胡椒、胡椒精油、胡椒油树脂中4种农药的慢性膳食摄入风险,结果远小于100%,表明其中的农药残留慢性摄入风险较小。Pepper(Piper nigrum L.),a vital spice,is abundant in flavor compounds such as piperine,sesquiterpenes,and terpenes.Pepper oleoresin and pepper essential oil are concentrated extracts of these flavor compounds,can offer enhanced culinary value.Both oleoresin and essential oils contain numerous organic compounds,including volatile oils,organic acids,alkaloids,and pigments,posing challenges in detecting pesticide residues in these products.This study introduced a method of gel permeation chromatography combined with QuEChERS gas chromatography tandem mass spectrometry(GPC-QuEChERS-GC-MS/MS)to detect pesticide residues in pepper oleoresin and essential oil,incorporating dietary risk assessment.The extraction of the pesticde was conducted using an ethyl acetate-cyclohexane(1:1,V/V)solvent system,followed by gel permeation chromatography and purification with graphitized carbon black(GCB)and N-propyl ethylenediamine(PSA)adsorbents.The multi-reaction monitoring(MRM)mode and matrix-matched calibration curves with internal standards were used for quantitative analysis.Under optimized conditions,the four pesticides have good linearity in the concentration of 3-100μg/L with the correlation coefficients exceeding 0.99.Recoveries at three spiked levels(0.1,0.5,1.0 mg/kg)range from 73%to 120%,suggesting high accuracy,and the relative standard deviations(RSDs)are below 20%,demonstrating good precision.The limits of detection are 0.04-0.10 mg/kg.A survey of 20 batches of black pepper,pepper essential oil,and pepper oleoresin on the market reveals maximum residue levels of metalaxyl,chlorpyrifos,permethrin,and cypermethrin at 1.236,0.954,2.087,and 1.174 mg/kg,respectively.A dietary risk assessment was conducted based on the median residue values determined in the samples.The results showed that the chronic dietary intake risks for four pesticides are significantly lower than 100%,indicating minimal dietary risks.This study not only provides a reliable and sensitive method for detecting pesticide residues in pepper extracts,but a

关 键 词：胡椒油树脂 胡椒精油 农药残留 气相色谱-串联质谱(GC-MS/MS) 慢性膳食摄入风险 

分 类 号：O657.63[理学—分析化学] S482.2[理学—化学]