超高效液相色谱-串联质谱法测定柑橘中11种保鲜剂残留

Determination of 11 Preservatives in Citrus by ultra performance liquid chromatography-tandem mass spectrometry

中文关键词:  超高效液相色谱-串联质谱法  保鲜剂  柑橘

英文关键词:ultra performance liquid chromatography-tandem mass spectrometry  preservatives  citrus

中文摘要:

      目的 建立超高效液相色谱-串联质谱法(ultra performance liquid chromatography-tandem mass spectrometry, UPLC-MS/MS)测定柑橘中多菌灵、噻菌灵、嘧霉胺、抑霉唑、甲基硫菌灵、咪鲜胺、对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯、对羟基苯甲酸丁酯和2,4-D的分析方法。方法 用乙腈作为提取剂, 振摇30 min后加入5 g氯化钠静置30 min, 上清液过滤待UPLC-MS/MS分析。采用ACQUITY UPLC BEH C18柱(2.1 mm×100 mm, 1.7 μm)进行液相色谱分离, 以0.1%甲酸0.5 mmol/L甲酸铵和甲醇作为流动相进行梯度洗脱。采用多反应监测模式进行质谱测定, 以基质配制标准溶液外标法定量。结果 11种保鲜剂在1.0~100 μg/L范围内线性关系良好(r2＞0.999), 方法最低检出限为0.03~0.21 μg/kg, 最低定量限为0.07~0.5 μg/kg; 在3个添加水平为1.0、5.0、10.0 μg/kg时, 回收率为75.1%~110.4%, 相对偏差为0.4%~9.8%。对26个柑橘样品进行分析, 多菌灵、咪鲜胺和对羟基苯甲酸丙酯在所有样品中均有检出, 2,4-D在25个样品中有检出, 嘧霉胺检出率最低, 仅在一个样品中检出。从品种上看, 柠檬的平均用药量最大(2285.51 μg/kg), 其次是橙类、橘类、柑类和金橘。结论 该方法简便、灵敏、准确, 适用于柑橘中多种保鲜剂的同时测定。

英文摘要:

      Objective To establish a method of determination of carbendazim, thiabendazole, pyrimethanil, imazalil, thiophanate, prochloraz, methylparaben, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate and 2,4-D. in citrus by ultra performance liquid chromatography-tandem mass spectrometry (UTS-MS/MS). Methods The sample was treated with acetonitrile as extractant. After shaking for 30 min, 5 g of sodium chloride was added and allowed to stand for 30 min. The liquid chromatographic separation was carried out using an ACQUITY UPLC BEH C18 column (2.1 mm × 100 mm, 1.7 μm) with gradient elution with 0.1% formic acid 0.5 mmol/L ammonium formate and methanol as mobile phase. Mass spectrometry was performed using a multi-reaction monitoring mode and quantified by matrix preparation of standard solution external standards. Results The linearity of 11 kinds of preservatives in the range of 1.0?100 μg/L was good (r2>0.999). The minimum detection limit of the method was 0.03?0.21 μg/kg, and the lowest limit of quantification was 0.07?0.5 μg/kg. At 1.0, 5.0, and 10.0 μg/kg, the recoveries were75.1% to 110.4%, and the relative standard deviations were 0.4% to 9.8%. Analysis of 26 citrus samples, carbendazim, prochloraz and propylparaben were detected in all samples, 2,4-D was detected in 25 samples, and pyrimethanil was detected in one sample. In terms of variety, the average dosage of lemon was the highest (2285.51 μg/kg), followed by orange, orange, citrus and kumquat. Conclusion This method is simple, sensitive and accurate, which is suitable for simultaneous determination of various preservatives in citrus.