超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法筛查鸡蛋中165种农药、兽药残留

Rapid screening of 165 kinds of pesticides and veterinary drugs residual in eggs by ultra performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry

中文关键词:  鸡蛋  农药兽药残留  超高效液相色谱-四极杆/静电场轨道阱高分辨质谱  筛查

英文关键词:egg  pesticides  veterinary drugs  residues  ultra performance liquid chromatography- quadrupole/electrostatic field orbitrap high resolution mass spectrometry  screening

中文摘要:

      目的 建立一种基于超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法快速筛查鸡蛋中165种农药、兽药残留的方法。方法 样品经过0.1%甲酸水溶液和乙腈溶液提取, 氯化钠和无水硫酸钠盐析, HyperSep Retain PEP固相萃取柱净化后, 采用ZORBAX Eclipse plus C18色谱柱分离, 以0.1%甲酸水(0.03%氨水)-0.1%甲酸乙腈(0.03%氨化乙腈)梯度洗脱, 分别在正/负离子模式下, 使用高分辨质谱Q-Exactive Plus采集数据。通过目标物信号响应、保留时间偏差、质量偏差等因素进行筛查和确证。结果 建立了165种农药、兽药的质谱数据库。165种农药、兽药在0.5~100.0 ng/mL范围内线性关系良好, 线性相关系数(r2)均大于0.99。检出限为0.5~3.0 μg/kg, 定量限为1.0~10.0 μg/kg; 在3个不同浓度添加水平下, 165种农药、兽药的平均回收率为41.36%~134.79%; 批内和批间的相对标准偏差(n=5)为1.02%~19.97%, 均小于20.00%。将该方法应用于100批鸡蛋样品的检测, 其中检出氟苯尼考阳性8份, 浓度为5.27~15.62 μg/kg; 检出恩诺沙星阳性5份, 浓度为10.53~26.52 μg/kg; 检出磺胺间甲氧嘧啶阳性2份, 浓度分别为12.66 μg/kg和19.49 μg/kg, 与国家标准检测结果相比, 本方法的筛查准确率为100%。结论 该方法简单、快速、准确, 可用于鸡蛋中农药、兽药残留的筛查和确证, 为政府监管鸡蛋质量安全提供技术支撑。

英文摘要:

      Objective To establish a rapid screening method for 165 kinds of pesticides and veterinary drugs in eggs based on ultra performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry. Methods The sample was extracted with 0.1% formic acid and acetonitrile, cleaned by HyperSep Retain PEP cartridge after salted out by sodium chloride and sodium sulfate anhydrous, separated by ZORBAX Eclipse plus C18 column, and then eluted by gradient with 0.1% formic acid water (0.03% ammonia water)-0.1% formic acid acetonitrile (0.03% ammoniated acetonitrile), using the high resolution mass spectrometry Q-Exactive plus to collect data in the positive/negative ion mode, screening and confirmation were carried out through target signal response, retention time deviation, quality deviation and other factors. Results The mass spectrum database of 165 kinds of pesticides and veterinary drugs was established, the results showed that 165 kinds of pesticides and veterinary drugs exhibited good linearity within the range of 0.5–100.0 ng/mL, and the correlation coefficient (r2) were all over 0.99. The limits of detection for this method were 0.5–3.0 μg/kg, the limits of quantitative were 1.0–10.0 μg/kg. Recovery test with 3 different addition contents showed the results in the range of 41.36%–134.79%, and all the relative standard deviation (n=5) were 1.02%–19.97%, less than 20.00%. At last the method was applied to detection of 100 egg samples, among which 8 samples contained florfenicol with the amount range from 5.27–15.62 μg/kg, 5 samples contained enrofloxacin with the amount range from 10.53–26.52 μg/kg, 2 samples contained sulfamonomethoxine with the amount 12.66 μg/kg and 19.49 μg/kg. Compared with the results of national standard method, the accuracy of this method for veterinary drugs screening was 100% in this study. Conclusion This method is simple, fast and accurate, and could be used for simultaneous screening and quantitative analysis of pesticides and veterinary drugs in eggs, providing technical support for government supervision of egg quality and safety.