色谱 ›› 2020, Vol. 38 ›› Issue (1): 120-126.DOI: 10.3724/SP.J.1123.2019.01051
收稿日期:
2019-01-30
出版日期:
2020-01-08
发布日期:
2020-12-11
通讯作者:
张卓旻,李攻科
作者简介:
李攻科, Tel:(020)84110922, E-mail:cesgkl@mail.sysu.edu.cn基金资助:
CHEN Zhengyi, LI Yunda, ZHANG Zhuomin(), LI Gongke()
Received:
2019-01-30
Online:
2020-01-08
Published:
2020-12-11
Contact:
ZHANG Zhuomin,LI Gongke
Supported by:
摘要:
将微热助吹扫捕集技术与超高压液相色谱-串联质谱(UHPLC-MS/MS)结合,建立了蔬菜中12种半挥发性农药残留的快速分析方法。系统优化了前处理条件,在10 min内即可完成样品前处理过程。12种半挥发性农药残留在各自范围内线性关系良好,相关系数(R2)为0.9918~0.9997;检出限为0.3~1.3 μg/kg,定量限为1.0~4.3 μg/kg。实际样品的加标回收率为80.0%~120.0%,日内和日间精密度均小于10%。该方法具有基质净化效果好、前处理过程简单和分析速度快等优点,可用于蔬菜中多种半挥发农药残留的同时快速分析。
陈正毅, 李运达, 张卓旻, 李攻科. 微热助吹扫捕集-超高压液相色谱-串联质谱法快速测定蔬菜中12种半挥发性农药残留[J]. 色谱, 2020, 38(1): 120-126.
CHEN Zhengyi, LI Yunda, ZHANG Zhuomin, LI Gongke. Rapid determination of 12 semi-volatile pesticide residues in vegetables by miniaturized thermal-assisted purge-and-trap coupled with ultra high pressure liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(1): 120-126.
No. | Pesticide | Retention time/min | Parent ion (m/z) | Product ion (m/z) | Q1 pre bias/V | CE/V | Q3 pre bias/V |
Q1/Q3 pre bias: Q1/Q3 prerod bias; CE: collision energy; * quantitative ion. | |||||||
1 | aphid (抗蚜威) | 0.88 | 239.0 | 72.2* | -11 | -25 | -17 |
239.0 | 182.0 | -12 | -16 | -18 | |||
2 | simazine (西玛津) | 2.12 | 201.9 | 132.0* | -10 | -19 | -13 |
201.9 | 96.1 | -10 | -22 | -10 | |||
3 | prometryne (扑草净) | 2.83 | 242.0 | 158.1* | -11 | -23 | -17 |
241.9 | 200.2 | -16 | -19 | -14 | |||
4 | carbaryl (西维因) | 2.84 | 201.9 | 145.2* | -10 | -11 | -15 |
201.9 | 127.1 | -10 | -27 | -24 | |||
5 | metalaxyl (甲霜灵) | 3.06 | 280.1 | 192.2 | -13 | -19 | -13 |
280.1 | 220.2* | -10 | -14 | -15 | |||
6 | triadimefon (三唑酮) | 4.19 | 294.0 | 69.2* | -11 | -21 | -13 |
294.0 | 197.1 | -14 | -15 | -13 | |||
7 | molinate (禾草敌) | 4.23 | 188.0 | 126.2* | -13 | -14 | -13 |
188.0 | 83.2 | -13 | -17 | -19 | |||
8 | acetochlor (乙草胺) | 4.61 | 270.1 | 224.1* | -10 | -11 | -15 |
270.1 | 148.2 | -10 | -19 | -16 | |||
9 | cadusafos (硫线磷) | 5.12 | 270.9 | 159.0* | -10 | -13 | -30 |
270.9 | 131.0 | -13 | -22 | -13 | |||
10 | tolclofos-methyl (甲基立枯磷) | 5.27 | 300.9 | 269.0* | -11 | -16 | -13 |
300.9 | 125.0 | -11 | -17 | -13 | |||
11 | chlorpyrifos (毒死蜱) | 5.98 | 351.5 | 199.5 | -17 | -18 | -30 |
351.5 | 97.0* | -17 | -32 | -18 | |||
12 | pendimethalin (二甲戊乐灵) | 5.99 | 282.1 | 212.1* | -14 | -11 | -14 |
282.1 | 194.1 | -13 | -19 | -20 |
表1 12种半挥发性农药残留的保留时间和质谱参数
Table 1 Retention times and MS/MS parameters of the 12 semi-volatile pesticide residues
No. | Pesticide | Retention time/min | Parent ion (m/z) | Product ion (m/z) | Q1 pre bias/V | CE/V | Q3 pre bias/V |
Q1/Q3 pre bias: Q1/Q3 prerod bias; CE: collision energy; * quantitative ion. | |||||||
1 | aphid (抗蚜威) | 0.88 | 239.0 | 72.2* | -11 | -25 | -17 |
239.0 | 182.0 | -12 | -16 | -18 | |||
2 | simazine (西玛津) | 2.12 | 201.9 | 132.0* | -10 | -19 | -13 |
201.9 | 96.1 | -10 | -22 | -10 | |||
3 | prometryne (扑草净) | 2.83 | 242.0 | 158.1* | -11 | -23 | -17 |
241.9 | 200.2 | -16 | -19 | -14 | |||
4 | carbaryl (西维因) | 2.84 | 201.9 | 145.2* | -10 | -11 | -15 |
201.9 | 127.1 | -10 | -27 | -24 | |||
5 | metalaxyl (甲霜灵) | 3.06 | 280.1 | 192.2 | -13 | -19 | -13 |
280.1 | 220.2* | -10 | -14 | -15 | |||
6 | triadimefon (三唑酮) | 4.19 | 294.0 | 69.2* | -11 | -21 | -13 |
294.0 | 197.1 | -14 | -15 | -13 | |||
7 | molinate (禾草敌) | 4.23 | 188.0 | 126.2* | -13 | -14 | -13 |
188.0 | 83.2 | -13 | -17 | -19 | |||
8 | acetochlor (乙草胺) | 4.61 | 270.1 | 224.1* | -10 | -11 | -15 |
270.1 | 148.2 | -10 | -19 | -16 | |||
9 | cadusafos (硫线磷) | 5.12 | 270.9 | 159.0* | -10 | -13 | -30 |
270.9 | 131.0 | -13 | -22 | -13 | |||
10 | tolclofos-methyl (甲基立枯磷) | 5.27 | 300.9 | 269.0* | -11 | -16 | -13 |
300.9 | 125.0 | -11 | -17 | -13 | |||
11 | chlorpyrifos (毒死蜱) | 5.98 | 351.5 | 199.5 | -17 | -18 | -30 |
351.5 | 97.0* | -17 | -32 | -18 | |||
12 | pendimethalin (二甲戊乐灵) | 5.99 | 282.1 | 212.1* | -14 | -11 | -14 |
282.1 | 194.1 | -13 | -19 | -20 |
图1 加标青瓜样品中12种半挥发性农药残留(8.0 μg/kg)的总离子流色谱图
Fig. 1 Total ion current chromatogram of the 12 semi-volatile pesticide residues (8.0 μg/kg) in a spiked cucumber sample Peaks. 1-12 were the same as that in Table 1.
图2 加热温度对12种半挥发性农药残留(10 μg/kg)回收率的影响(n=3)
Fig. 2 Effect of heating temperatures on the recoveries of the 12 semi-volatile pesticide residues (10.0 μg/kg)(n=3)
图4 氮气流速对12种半挥发性农药残留(10 μg/kg)回收率的影响(n=3)
Fig. 4 Effect of nitrogen flow speeds on the recoveries of the 12 semi-volatile pesticide residues (10 μg/kg) (n=3)
Pesticide | Regression equation | Linear range/(μg/kg) | R2 | LOD/(μg/kg) | LOQ/(μg/kg) |
y: peak area; x: content, μ g/kg. | |||||
Aphid | y=9.62×106x-7.99×106 | 2.0-100.0 | 0.9996 | 0.3 | 1.0 |
Simazine | y=1.89×106x-1.36×106 | 2.0-100.0 | 0.9948 | 0.5 | 1.7 |
Prometryne | y=1.42×107x-5.17×106 | 2.0-100.0 | 0.9997 | 0.4 | 1.3 |
Carbaryl | y=1.95×105x-9.82×105 | 5.0-200.0 | 0.9966 | 1.0 | 3.3 |
Metalaxyl | y=7.06×106x-1.47×107 | 2.0-100.0 | 0.9941 | 0.4 | 1.3 |
Triadimefon | y=1.30×106x-6.60×106 | 5.0-200.0 | 0.9918 | 1.1 | 3.7 |
Molinate | y=1.43×106x-3.39×106 | 5.0-200.0 | 0.9918 | 0.9 | 3.0 |
Acetochlor | y=6.54×105x-1.66×106 | 5.0-200.0 | 0.9990 | 0.8 | 2.7 |
Cadusafos | y=4.63×106x-4.80×106 | 5.0-200.0 | 0.9971 | 1.1 | 3.7 |
Tolclofos-methyl | y=3.13×105x-7.85×105 | 5.0-200.0 | 0.9969 | 1.2 | 4.0 |
Chlorpyrifos | y=4.59×105x-9.70×105 | 5.0-200.0 | 0.9968 | 1.3 | 4.3 |
Pendimethalin | y=1.86×106x-4.63×105 | 2.0-100.0 | 0.9951 | 0.3 | 1.0 |
表2 12种半挥发性农药残留的回归方程、线性范围、相关系数、检出限和定量限
Table 2 Regression equations, linear ranges, correlation coefficients (R2), LODs and LOQs of the 12 semi-volatile pesticide residues
Pesticide | Regression equation | Linear range/(μg/kg) | R2 | LOD/(μg/kg) | LOQ/(μg/kg) |
y: peak area; x: content, μ g/kg. | |||||
Aphid | y=9.62×106x-7.99×106 | 2.0-100.0 | 0.9996 | 0.3 | 1.0 |
Simazine | y=1.89×106x-1.36×106 | 2.0-100.0 | 0.9948 | 0.5 | 1.7 |
Prometryne | y=1.42×107x-5.17×106 | 2.0-100.0 | 0.9997 | 0.4 | 1.3 |
Carbaryl | y=1.95×105x-9.82×105 | 5.0-200.0 | 0.9966 | 1.0 | 3.3 |
Metalaxyl | y=7.06×106x-1.47×107 | 2.0-100.0 | 0.9941 | 0.4 | 1.3 |
Triadimefon | y=1.30×106x-6.60×106 | 5.0-200.0 | 0.9918 | 1.1 | 3.7 |
Molinate | y=1.43×106x-3.39×106 | 5.0-200.0 | 0.9918 | 0.9 | 3.0 |
Acetochlor | y=6.54×105x-1.66×106 | 5.0-200.0 | 0.9990 | 0.8 | 2.7 |
Cadusafos | y=4.63×106x-4.80×106 | 5.0-200.0 | 0.9971 | 1.1 | 3.7 |
Tolclofos-methyl | y=3.13×105x-7.85×105 | 5.0-200.0 | 0.9969 | 1.2 | 4.0 |
Chlorpyrifos | y=4.59×105x-9.70×105 | 5.0-200.0 | 0.9968 | 1.3 | 4.3 |
Pendimethalin | y=1.86×106x-4.63×105 | 2.0-100.0 | 0.9951 | 0.3 | 1.0 |
Pesticide | Added/ (μg/kg) | Found/ (μg/kg) | Recovery/ % | RSDs/% | |
Intra- day | Inter- day | ||||
Aphid | 2.0 | 2.2 | 110.0 | 5.5 | 5.4 |
4.0 | 4.3 | 107.5 | 7.7 | 8.9 | |
8.0 | 8.7 | 108.8 | 3.8 | 8.9 | |
Simazine | 2.0 | 1.7 | 85.0 | 8.6 | 4.3 |
4.0 | 3.6 | 90.0 | 6.7 | 8.7 | |
8.0 | 6.9 | 86.3 | 7.9 | 7.5 | |
Prometryne | 2.0 | 2.1 | 105.0 | 4.2 | 3.7 |
4.0 | 3.4 | 85.0 | 7.1 | 7.1 | |
8.0 | 9.6 | 120.0 | 3.5 | 3.3 | |
Carbaryl | 5.0 | 4.2 | 84.0 | 8.4 | 3.6 |
10.0 | 8.3 | 83.0 | 6.4 | 8.8 | |
20.0 | 21.6 | 108.0 | 4.2 | 3.9 | |
Metalaxyl | 2.0 | 2.4 | 120.0 | 8.4 | 6.4 |
4.0 | 4.7 | 117.5 | 3.8 | 3.2 | |
8.0 | 8.7 | 108.8 | 3.0 | 6.7 | |
Triadimefon | 5.0 | 4.0 | 80.0 | 9.0 | 3.1 |
10.0 | 8.0 | 80.0 | 8.3 | 9.0 | |
20.0 | 16.6 | 83.0 | 3.2 | 6.5 | |
Molinate | 5.0 | 5.9 | 118.0 | 8.2 | 7.2 |
10.0 | 8.5 | 85.0 | 3.0 | 6.3 | |
20.0 | 16.0 | 80.0 | 3.1 | 7.0 | |
Acetochlor | 5.0 | 4.4 | 88.0 | 3.1 | 8.1 |
10.0 | 8.1 | 81.0 | 7.6 | 3.9 | |
20.0 | 19.5 | 97.5 | 3.4 | 8.5 | |
Cadusafos | 5.0 | 5.9 | 118.0 | 8.8 | 5.2 |
10.0 | 12.0 | 120.0 | 8.4 | 3.2 | |
20.0 | 20.4 | 102.0 | 8.8 | 5.2 | |
Tolclofos-methyl | 5.0 | 5.2 | 104.0 | 5.3 | 4.9 |
10.0 | 9.0 | 90.0 | 5.4 | 6.0 | |
20.0 | 18.8 | 94.0 | 8.1 | 9.3 | |
Chlorpyrifos | 5.0 | 4.2 | 84.0 | 3.0 | 4.9 |
10.0 | 8.0 | 80.0 | 8.6 | 3.3 | |
20.0 | 20.2 | 101.0 | 5.6 | 7.5 | |
Pendimethalin | 2.0 | 2.1 | 105.0 | 8.2 | 7.2 |
4.0 | 4.8 | 120.0 | 4.5 | 3.7 | |
8.0 | 6.8 | 85.0 | 3.2 | 9.0 |
表3 生菜样品中12种半挥发性农药残留的加标回收率和RSD(n=3)
Table 3 Spiked recoveries and RSDs of the 12 semi- volatile pesticide residues in cole samples (n=3)
Pesticide | Added/ (μg/kg) | Found/ (μg/kg) | Recovery/ % | RSDs/% | |
Intra- day | Inter- day | ||||
Aphid | 2.0 | 2.2 | 110.0 | 5.5 | 5.4 |
4.0 | 4.3 | 107.5 | 7.7 | 8.9 | |
8.0 | 8.7 | 108.8 | 3.8 | 8.9 | |
Simazine | 2.0 | 1.7 | 85.0 | 8.6 | 4.3 |
4.0 | 3.6 | 90.0 | 6.7 | 8.7 | |
8.0 | 6.9 | 86.3 | 7.9 | 7.5 | |
Prometryne | 2.0 | 2.1 | 105.0 | 4.2 | 3.7 |
4.0 | 3.4 | 85.0 | 7.1 | 7.1 | |
8.0 | 9.6 | 120.0 | 3.5 | 3.3 | |
Carbaryl | 5.0 | 4.2 | 84.0 | 8.4 | 3.6 |
10.0 | 8.3 | 83.0 | 6.4 | 8.8 | |
20.0 | 21.6 | 108.0 | 4.2 | 3.9 | |
Metalaxyl | 2.0 | 2.4 | 120.0 | 8.4 | 6.4 |
4.0 | 4.7 | 117.5 | 3.8 | 3.2 | |
8.0 | 8.7 | 108.8 | 3.0 | 6.7 | |
Triadimefon | 5.0 | 4.0 | 80.0 | 9.0 | 3.1 |
10.0 | 8.0 | 80.0 | 8.3 | 9.0 | |
20.0 | 16.6 | 83.0 | 3.2 | 6.5 | |
Molinate | 5.0 | 5.9 | 118.0 | 8.2 | 7.2 |
10.0 | 8.5 | 85.0 | 3.0 | 6.3 | |
20.0 | 16.0 | 80.0 | 3.1 | 7.0 | |
Acetochlor | 5.0 | 4.4 | 88.0 | 3.1 | 8.1 |
10.0 | 8.1 | 81.0 | 7.6 | 3.9 | |
20.0 | 19.5 | 97.5 | 3.4 | 8.5 | |
Cadusafos | 5.0 | 5.9 | 118.0 | 8.8 | 5.2 |
10.0 | 12.0 | 120.0 | 8.4 | 3.2 | |
20.0 | 20.4 | 102.0 | 8.8 | 5.2 | |
Tolclofos-methyl | 5.0 | 5.2 | 104.0 | 5.3 | 4.9 |
10.0 | 9.0 | 90.0 | 5.4 | 6.0 | |
20.0 | 18.8 | 94.0 | 8.1 | 9.3 | |
Chlorpyrifos | 5.0 | 4.2 | 84.0 | 3.0 | 4.9 |
10.0 | 8.0 | 80.0 | 8.6 | 3.3 | |
20.0 | 20.2 | 101.0 | 5.6 | 7.5 | |
Pendimethalin | 2.0 | 2.1 | 105.0 | 8.2 | 7.2 |
4.0 | 4.8 | 120.0 | 4.5 | 3.7 | |
8.0 | 6.8 | 85.0 | 3.2 | 9.0 |
图5 采用(a)微型热助吹扫捕集前处理方法和(b)QuEChERS方法时加标生菜样品(50 μg/kg)的质谱图
Fig. 5 Mass spectra of the spiked cole samples (50 μg/kg) by (a) miniaturized thermal-assisted purge and (b) QuEChERS methods Nos. 1-12 were the same as that in Table 1.
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