改进QuEChERS-液质联用法测定黄精中23种农药残留

doi:10.16178/j.issn.0528-9017.20230109

摘要/Abstract

摘要：

建立黄精中氧乐果、多菌灵、噻虫嗪等23种农药残留的QuEChERS快速样品处理结合液相色谱-串联质谱检测方法,对净化条件、质谱条件等进行了优化。样品用1%乙酸乙腈提取,用900 mg无水硫酸镁、300 mg N-丙基乙二胺、300 mg十八烷基硅烷键合硅胶和100 mg硅胶净化。结果表明,23种农药多残留的回收率均在75.61%~114.52%,线性关系良好,相关系数在0.995 5~0.999 9,相对标准偏差小于9.99%,测定低限均不超过《中华人民共和国药典》(2020年版)规定的定量限。

关键词: 黄精, QuEChERS, 液相色谱-串联质谱

Abstract:

A QuEChERS rapid sample processing combined with liquid chromatography-tandem mass spectrometry detection method was established for 23 pesticide residues in Polygonatum sibiricum, including omethoate, carbendazim, and thiamethoxam. Purification and mass spectrometry conditions were optimized. The sample was extracted with 1% acetonitrile acetate and purified with 900 mg anhydrous magnesium sulfate, 300 mg N-propylethylenediamine, 300 mg octadecylsilane bonded silica gel, and 100 mg silica gel. The results showed that the recovery rates of 23 pesticide residues were all between 75.61% and 114.52%, with a good linear relationship. The correlation coefficient was between 0.995 5 and 0.999 9, and the relative standard deviation was less than 9.99%. The lower limit of determination was not exceed the quantitative limit specified in the Pharmacopoeia of the People's Republic of China (2020 version).

Key words: Polygonatum sibiricum, QuEChERS, liquid chromatography-tandem mass spectrometry

中图分类号:

S567

何华军, 张辉, 夏丽敏, 王远远. 改进QuEChERS-液质联用法测定黄精中23种农药残留[J]. 浙江农业科学, 2024, 65(2): 420-426.

Huajun HE, Hui ZHANG, Limin XIA, Yuanyuan WANG. Improved QuEChERS liquid chromatography-mass spectrometry for the determination of 23 pesticide residues in Polygonatum sibiricum[J]. Journal of Zhejiang Agricultural Sciences, 2024, 65(2): 420-426.

图/表 6

参考文献 16

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序号	农药名称	保留时间/min	母离子(m/z)	锥孔电压/V	子离子(m/z)	碰撞电压/V
1	氧乐果	1.92	214.1	26	183.1^*,125.1	11,22
2	多菌灵	2.39	192.1	33	132.1^*,160.1	28,18
3	噻虫嗪	2.75	292.0	25	211.2^*,132.0	10,20
4	吡虫啉	3.18	256.1	34	209.1^*,175.1	15,20
5	乐果	3.26	230.1	24	125.0^*,199.0	20,10
6	啶虫脒	3.35	223.0	34	126.0^*,56.1	15,20
7	嘧霉胺	4.99	200.0	51	107.0^*,82.0	24,24
8	烯酰吗啉	5.11,5.21	388.1	41	300.9^*,165.0	20,30
9	腈菌唑	5.47	289.1	25	70.2^*,125.1	30,15
10	嘧菌酯	5.51	404.0	28	372.0^*,329.0	15,30
11	氟环唑	5.55	330.0	15	121.0^*,101.0	22,50
12	联苯肼酯	5.72	301.1	25	198.0^*,170.0	10,20
13	马拉硫磷	5.81	331.0	30	126.9^*,98.9	12,25
14	三唑磷	5.86	314.1	22	161.9^*,118.9	18,35
15	咪鲜胺	5.87	376.0	20	307.9^*,70.1	12,25
16	倍硫磷	6.30	279.0	25	168.9^*,104.9	18,25
17	二嗪农	6.50	305.1	31	169.0^*,96.9	22,35
18	辛硫磷	6.56	299.0	12	129.0^*,153.0	13,7
19	茚虫威	6.62	528.1	30	202.9^*,217.9	40,25
20	丙溴磷	6.76	372.9	36	302.6^*,127.9	20,40
21	增效醚	7.03	356.3	20	176.9^*,119.0	10,35
22	毒死蜱	7.23	350.1	25	197.9^*,97.0	19,33
23	哒螨灵	7.70	365.1	5	147.1^*,309.1	24,12

序号	农药名称	保留时间/min	母离子(m/z)	锥孔电压/V	子离子(m/z)	碰撞电压/V
1	氧乐果	1.92	214.1	26	183.1^*,125.1	11,22
2	多菌灵	2.39	192.1	33	132.1^*,160.1	28,18
3	噻虫嗪	2.75	292.0	25	211.2^*,132.0	10,20
4	吡虫啉	3.18	256.1	34	209.1^*,175.1	15,20
5	乐果	3.26	230.1	24	125.0^*,199.0	20,10
6	啶虫脒	3.35	223.0	34	126.0^*,56.1	15,20
7	嘧霉胺	4.99	200.0	51	107.0^*,82.0	24,24
8	烯酰吗啉	5.11,5.21	388.1	41	300.9^*,165.0	20,30
9	腈菌唑	5.47	289.1	25	70.2^*,125.1	30,15
10	嘧菌酯	5.51	404.0	28	372.0^*,329.0	15,30
11	氟环唑	5.55	330.0	15	121.0^*,101.0	22,50
12	联苯肼酯	5.72	301.1	25	198.0^*,170.0	10,20
13	马拉硫磷	5.81	331.0	30	126.9^*,98.9	12,25
14	三唑磷	5.86	314.1	22	161.9^*,118.9	18,35
15	咪鲜胺	5.87	376.0	20	307.9^*,70.1	12,25
16	倍硫磷	6.30	279.0	25	168.9^*,104.9	18,25
17	二嗪农	6.50	305.1	31	169.0^*,96.9	22,35
18	辛硫磷	6.56	299.0	12	129.0^*,153.0	13,7
19	茚虫威	6.62	528.1	30	202.9^*,217.9	40,25
20	丙溴磷	6.76	372.9	36	302.6^*,127.9	20,40
21	增效醚	7.03	356.3	20	176.9^*,119.0	10,35
22	毒死蜱	7.23	350.1	25	197.9^*,97.0	19,33
23	哒螨灵	7.70	365.1	5	147.1^*,309.1	24,12

农药名称	线性方程	R²	基质效应/%	LOD/(μg·kg^-1)	LOQ/(μg·kg^-1)
氧乐果	y=1 898.3x-16.216 1	0.997 7	2.91	0.24	0.82
多菌灵	y=1 336.33x-171.224 0	0.995 6	6.33	0.08	0.27
噻虫嗪	y=2 618.3x+283.543 0	0.999 8	4.16	0.13	0.43
吡虫啉	y=1 738.35x-113.550 0	0.999 5	-22.86	0.36	1.20
乐果	y=8 120.03x+140.343 0	0.999 8	-12.51	0.10	0.35
啶虫脒	y=26 792.8x-258.984 0	0.999 9	-0.20	0.03	0.10
嘧霉胺	y=3 223.32x-362.388 0	0.995 6	67.79	0.36	1.19
烯酰吗啉	y=18 459.1x-1 108.520 0	0.999 9	16.44	0.04	0.14
腈菌唑	y=10 767.1x-213.834 0	0.999 6	-4.02	0.02	0.08
嘧菌酯	y=51 843.5x-612.971 0	0.999 9	-8.22	0.01	0.05
氟环唑	y=18 256.1x-1 758.520 0	0.999 8	-1.67	0.16	0.53
联苯肼酯	y=4 870.83x+435.764 0	0.999 3	20.56	0.08	0.27
马拉硫磷	y=6 532.72x+451.679 0	0.999 5	-1.84	0.16	0.53
三唑磷	y=69 429.8x+4 170.660 0	0.999 7	2.13	0.01	0.04
咪鲜胺	y=7 518.1x+61.562 5	0.999 5	0.52	0.06	0.19
倍硫磷	y=1 710.76x+651.107 0	0.997 0	1.59	0.64	2.12
二嗪农	y=53 511.6x+1 903.970 0	0.999 9	-0.37	0.02	0.05
辛硫磷	y=1 890.07x-336.372 0	0.998 3	-2.17	0.99	3.29
茚虫威	y=3 253.7x+116.023 0	0.999 2	3.06	0.19	0.64
丙溴磷	y=5 702.88x-19.033 7	0.999 0	1.04	0.03	0.11
增效醚	y=30 484.8x+2 278.420 0	0.999 7	-4.34	0.05	0.15
毒死蜱	y=1 172.26x+344.739 0	0.995 5	-5.95	0.31	1.04
哒螨灵	y=29 998.7x+2 136.110 0	0.999 8	-1.26	0.07	0.22

农药名称	线性方程	R²	基质效应/%	LOD/(μg·kg^-1)	LOQ/(μg·kg^-1)
氧乐果	y=1 898.3x-16.216 1	0.997 7	2.91	0.24	0.82
多菌灵	y=1 336.33x-171.224 0	0.995 6	6.33	0.08	0.27
噻虫嗪	y=2 618.3x+283.543 0	0.999 8	4.16	0.13	0.43
吡虫啉	y=1 738.35x-113.550 0	0.999 5	-22.86	0.36	1.20
乐果	y=8 120.03x+140.343 0	0.999 8	-12.51	0.10	0.35
啶虫脒	y=26 792.8x-258.984 0	0.999 9	-0.20	0.03	0.10
嘧霉胺	y=3 223.32x-362.388 0	0.995 6	67.79	0.36	1.19
烯酰吗啉	y=18 459.1x-1 108.520 0	0.999 9	16.44	0.04	0.14
腈菌唑	y=10 767.1x-213.834 0	0.999 6	-4.02	0.02	0.08
嘧菌酯	y=51 843.5x-612.971 0	0.999 9	-8.22	0.01	0.05
氟环唑	y=18 256.1x-1 758.520 0	0.999 8	-1.67	0.16	0.53
联苯肼酯	y=4 870.83x+435.764 0	0.999 3	20.56	0.08	0.27
马拉硫磷	y=6 532.72x+451.679 0	0.999 5	-1.84	0.16	0.53
三唑磷	y=69 429.8x+4 170.660 0	0.999 7	2.13	0.01	0.04
咪鲜胺	y=7 518.1x+61.562 5	0.999 5	0.52	0.06	0.19
倍硫磷	y=1 710.76x+651.107 0	0.997 0	1.59	0.64	2.12
二嗪农	y=53 511.6x+1 903.970 0	0.999 9	-0.37	0.02	0.05
辛硫磷	y=1 890.07x-336.372 0	0.998 3	-2.17	0.99	3.29
茚虫威	y=3 253.7x+116.023 0	0.999 2	3.06	0.19	0.64
丙溴磷	y=5 702.88x-19.033 7	0.999 0	1.04	0.03	0.11
增效醚	y=30 484.8x+2 278.420 0	0.999 7	-4.34	0.05	0.15
毒死蜱	y=1 172.26x+344.739 0	0.995 5	-5.95	0.31	1.04
哒螨灵	y=29 998.7x+2 136.110 0	0.999 8	-1.26	0.07	0.22

农药名称	加标浓度10 μg·kg^-1		加标浓度25 μg·kg^-1		加标浓度100 μg·kg^-1
农药名称	回收率/%	RSD/%	回收率/%	RSD/%	回收率/%	RSD/%
氧乐果	83.36	4.73	75.61	3.58	82.29	2.34
多菌灵	100.17	5.45	95.03	5.00	93.66	3.70
噻虫嗪	95.82	3.66	96.84	2.94	98.83	2.85
吡虫啉	101.08	9.99	95.99	2.39	98.44	2.15
乐果	98.40	3.26	100.17	1.30	97.41	1.02
啶虫脒	100.66	1.52	101.16	0.96	103.15	0.95
嘧霉胺	101.00	5.09	82.97	2.31	92.20	3.68
烯酰吗啉	95.38	2.34	95.05	1.52	94.17	1.71
腈菌唑	96.08	3.54	97.90	1.24	97.83	0.64
嘧菌酯	95.98	1.93	98.18	1.30	100.30	1.07
氟环唑	99.06	2.89	97.11	1.63	95.33	1.14
联苯肼酯	89.55	2.67	95.91	1.57	94.89	2.43
马拉硫磷	92.73	2.21	96.97	3.21	96.96	2.11
三唑磷	98.33	1.26	100.45	1.01	99.20	0.78
咪鲜胺	98.68	3.53	97.43	1.97	97.36	1.64
倍硫磷	108.28	4.39	99.67	3.09	91.97	3.90
二嗪农	99.86	1.71	98.71	0.61	98.65	1.01
辛硫磷	114.52	8.76	101.38	2.58	97.71	4.43
茚虫威	98.95	6.39	100.88	2.10	101.88	1.54
丙溴磷	104.56	1.94	100.39	2.30	98.03	1.81
增效醚	96.49	1.37	98.20	1.47	96.57	0.64
毒死蜱	96.99	8.06	92.88	7.08	96.87	2.73
哒螨灵	98.29	2.01	97.38	1.60	97.36	1.33