Detection of nine herbicide residues in Angelica sinensis by QuEChERS-GC-MS
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摘要:目的
建立当归中除草剂的残留分析方法。
方法阿特拉津、异恶草酮、乙草胺、扑草净、异丙甲草胺、二甲戊灵、丁草胺、丙草胺和乙氧氟草醚9种除草剂残留分析采用QuEChERS方法结合气相色谱-质谱联用仪。样品用乙腈提取，采用N–丙基乙二胺(PSA)和石墨化炭黑(GCB)净化，选择离子监测模式(SIM)进行检测，外标法定量。对影响提取和净化的参数进行优化。
结果在0.01~5.00 mg·L–1的范围内，各除草剂的峰面积与质量浓度呈良好的线性关系。在添加量分别为0.01和0.10 mg·kg–1的水平下，9种除草剂在当归样品中的平均回收率为74.58%~96.37%，相对标准偏差均低于11.73%，各除草剂的检出限范围为0.52~6.60 μg·kg–1。
结论该方法简单、快速、有效，能够用于实际当归样品中多种除草剂的残留检测。
Abstract:ObjectiveTo establish a method for analyzing herbicide residues in Angelica sinensis.
MethodThe residues of nine herbicides, including fenamine, clomazone, acetochlor, prometryn, metolachlor, pendimethalin, butachlor, pretilachlor and oxyfluorfen were analyzed by QuEChERS combined with GC-MS. Samples were extracted with acetonitrile and cleaned up using primary secondary amine (PSA) and graphitized carbon black (GCB). Nine herbicides were detected using the selective ion monitoring (SIM) mode and quantified with external standards. Parameters which influenced extraction and purification efficiency were optimized.
ResultThere were good linear relationships between herbicide concentration and detected peak area within the range from 0.01 to 5.00 mg·L-1 for all nine herbicides. The average recovery rates of nine herbicides in A. sinensis were from 74.58% to 96.37% at the addition levels of 0.01 and 0.10 mg·kg-1, with relative standard deviation less than 11.73%. The detection limits of nine herbicides were from 0.52 to 6.60 μg·kg-1.
ConclusionThis detection method is simple, fast and effective, and can be used practically to detect a variety of herbicides in A. sinensis samples.
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Keywords:
- QuEChERS /
- herbicide /
- Angelica sinensis /
- GC-MS /
- pesticide residue
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图 1 除草剂混合标样色谱图
1：阿特拉津；2：异恶草酮；3：乙草胺；4：扑草净；5：异丙甲草胺；6：二甲戊灵；7：丁草胺；8：丙草胺；9：乙氧氟草醚。
Figure 1. Chromatograms of mixed standard solution
表 1 9种除草剂的保留时间和特征离子
Table 1 Retention time and characteristic ions of nine herbicides
目标组分 t保留/min t开始/min 特征离子(m/z) 阿特拉津 6.356 3.000 200.0，204.0 异恶草酮 6.482 3.000 200.0，204.0 乙草胺 7.634 7.000 223.0 扑草净 7.981 7.800 184.0, 241.0 异丙甲草胺 8.687 8.300 162.0, 238.0 二甲戊灵 9.526 9.000 252.0 丁草胺 10.570 9.750 176.0 丙草胺 11.155 9.750 176.0 乙氧氟草醚 11.467 11.300 252.0 
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表 2 方法的检出限、相关系数、线性范围
Table 2 Limit of detection, correlation coefficient and linear range of this method
除草剂 线性范围/(mg·L-1) 线性方程1) 相关系数(r) 检出限/(μg·kg-1) 阿特拉津 0.01~5.00 y=206 977x–9 799 0.999 3 0.52 异恶草酮 0.01~5.00 y=280 281x–17 483 0.998 9 0.57 乙草胺 0.01~5.00 y=70 024x–5 493 0.999 1 2.90 扑草净 0.01~5.00 y=237 126x–10 159 0.999 5 0.75 异丙甲草胺 0.01~5.00 y=513 152x–37 270 0.998 5 0.54 二甲戊灵 0.01~5.00 y=282 124x–44 980 0.998 6 0.96 丁草胺 0.01~5.00 y=180 091x–19 806 0.998 2 1.40 丙草胺 0.01~5.00 y=164 374x–20 539 0.998 7 1.90 乙氧氟草醚 0.01~5.00 y=70 968x–15 898 0.998 8 6.60 1) x 表示除草剂质量浓度，y 表示峰面积。
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表 3 9 种除草剂在当归样品中的回收率和相对标准偏差
Table 3 Recovery rates and relative standard deviations of nine herbicides in Angelica sinensis %
除草剂 添加0.01 mg·kg-1 添加0.10 mg·kg-1 回收率 相对标准偏差 回收率 相对标准偏差 阿特拉津 82.04 9.74 95.70 6.30 异恶草酮 83.27 11.73 96.27 6.06 乙草胺 85.66 6.77 85.20 8.29 扑草净 74.58 8.38 85.65 5.92 异丙甲草胺 81.38 8.63 88.28 8.74 二甲戊灵 86.89 7.94 87.60 7.33 丁草胺 81.82 4.64 96.37 6.69 丙草胺 77.71 8.24 89.30 6.72 乙氧氟草醚 79.36 7.63 92.09 5.42
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