噁唑酰草胺及其代谢物在水稻上的残留

何红梅; 徐玲英; 张昌朋; 王祥云; 李艳杰; 赵学平

doi:10.16801/j.issn.1008-7303.2021.0185

噁唑酰草胺及其代谢物在水稻上的残留

doi: 10.16801/j.issn.1008-7303.2021.0185

1.
省部共建农产品质量安全危害因子与风险防控国家重点实验室 (筹)，农业农村部农药残留检测重点实验室，浙江省农业科学院农产品质量安全与营养研究所，杭州 310021

基金项目: 浙江省分析测试基金项目 (2018C37013).

详细信息

通讯作者:
何红梅，hehongmei53@163.com.

中图分类号: TQ450.2；O657.63
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出版历程
- 收稿日期: 2021-07-02
- 录用日期: 2021-10-24
- 网络出版日期: 2022-01-11
- 刊出日期: 2022-04-01

Residues of metamifop and its metabolites in paddy rice

1.
State Key Laboratory for Managing Biotic and Chemical Threats to the Quality and Safety of Agro-Products, Ministry of Agriculture and Rural Affairs Key Laboratory for Pesticide Residue Detection; Institute of Agro-Product Safety and Nutrition, Zhejiang Academy of Agricultural Sciences, Hangzhou 310021, China

Funds: The Analysis and Testing Technology Projects of Zhejiang (2018C37013).

摘要

摘要: 为探明噁唑酰草胺及其3个代谢物 (N-(2-氟苯基)-2-(4-羟基苯氧基)-N-甲基丙酰胺(HPFMPA)、N-(2-氟苯基)-2-羟基-N-甲基丙酰胺(HFMPA)和6-氯-苯并噁唑酮(6-CBO)) 在水稻上的最终残留量，在我国10个主要水稻产区开展了噁唑酰草胺的田间残留试验。建立了糙米、稻壳和稻秆中噁唑酰草胺及其代谢物残留量的检测方法，评估了方法的基质效应。样品经乙腈提取、盐析、C₁₈固相萃取小柱净化后采用超高效液相色谱-串联质谱法 (UPLC-MS/MS) 测定，6-CBO采用电喷雾负离子模式，其他采用电喷雾正离子模式。糙米、稻壳和稻秆中3档添加水平 (0.01、0.1和2.0 mg/kg) 下的平均回收率为79%~108%，相对标准偏差为0.9%~10.8%。噁唑酰草胺及其代谢物在糙米、稻壳和稻秆中的定量限(LOQ)均为0.01 mg/kg，在0.0005~0.02 mg/L质量浓度范围内，溶剂标准曲线和基质匹配标准曲线的线性关系均良好 (r>0.9941)，无明显基质效应。残留试验结果表明：噁唑酰草胺及其代谢物在糙米和稻壳中的残留量均<0.01 mg/kg，糙米中的残留量低于我国最大残留限量 (MRL) 值 (0.05 mg/kg)；HFMPA在稻秆中的残留量为<0.01~0.098 mg/kg，其余3个化合物在稻秆中的残留量均低于LOQ。建议20% 噁唑•灭草松微乳剂 (ME，其中噁唑酰草胺质量分数为3.3%) 在水稻上施用时，可按最高施药剂量 (有效成分720 g/hm²，噁唑酰草胺为118.8 g/hm²) 施药1次。
- 噁唑酰草胺 /
- 代谢物 /
- 水稻 /
- 残留 /
- 超高效液相色谱-串联质谱
Abstract: In this work, a method for the determination of the residues of metamifop and its three metabolites in samples of brown rice, paddy hull and rice straw was validated based on ultra performance liquid chromatography-tandem mass spectrometry. The three metabolites were N-(2-fluorophenyl)-2-hydroxy-N-methylpropionamide (HFMPA), N-(2-fluorophenyl)-2-(4-hydroxyphenoxy)-N-methylpropionamide (HPFMPA) and 6-chloro-3H-benzooxazol-2-one (6-CBO). The detection of 6-CBO was performed by tandem mass spectrometry with electrospray ionization in negative mode (ESI^-), and the other three analytes were determined in positive mode (ESI⁺). The samples of paddy rice were extracted with acetonitrile by an oscillator, and cleaned up by C₁₈ SPE cartridges. The method was validated and the matrix effects were evaluated. The method was applied to detect real final residue samples in the field trials. and the matrix effects were estimated. The average recoveries of metamifop and its metabolites in brown rice, paddy hull and rice straw at three spiked levels (0.01, 0.1 and 2.0 mg/kg) were in the range of 79%-108% with good precision (RSD<10.8%). Satisfactory linear relationships of metamifop, HFMPA, HPFMPA and 6-CBO were obtained in the range of 0.0005-0.02 mg/L with the correlation coefficient (r) over 0.9941. Limits of quantifications (LOQs) of metamifop, HFMPA, HPFMPA and 6-CBO in brown rice, paddy hull and rice straw were 0.01 mg/kg. To investigate the final residues of metamifop and its metabolites in paddy rice, the field trials were conducted in paddy rice in ten Provinces in China. The final residues of metamifop, HFMPA, HPFMPA and 6-CBO in brown rice and paddy hull were all below 0.01 mg/kg , which were lower than the maximum residue limit (MRL) of metamifop in brown rice (0.05 mg/kg) established in China. The residues of HFMPA were found in rice straw in the range of < 0.01 mg/kg-0.098 mg/kg, while the final residues of metamifop, HPFMPA and 6-CBO in rice straw were all below LOQ. It is recommended that 20% metamifop + bentazone micro-emulsion (ME, 3.3% metamifop) could be applied at the highest application dosage of 720 g a.i./hm² (metamifop 118.8 g a.i./hm² ) in rice and be applied only once.
- metamifop /
- metabolite /
- paddy rice /
- residue /
- ultra-performance liquid chromatography-tandem mass spectrometry

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1 噁唑酰草胺及其3个代谢物的结构式

1. The structural formula of metamifop and its metabolites HPFMPA, HFMPA and 6-CBO

下载: 全尺寸图片幻灯片

图 1 噁唑酰草胺色谱图

A-1~A-7分别为标样 (0.00167 mg/L) 、糙米空白及添加 (0.01 mg/kg) 、稻壳空白及添加 (0.01 mg/kg) 和稻秆空白及添加 (0.01 mg/kg) 色谱图。

Figure 1. Chromatograms of metamifop

Chromatograms of metamifop (A-1~A-7, standard of 0.00167 mg/L, brown rice blank and spiked (0.01 mg/kg)， paddy hull blank and spiked (0.01 mg/kg)，rice straw blank and spiked (0.01mg/kg).

下载: 全尺寸图片幻灯片

图 4 6-CBO色谱图

D-1~D-7分别为标样 (0.00167 mg/L) 、糙米空白及添加 (0.01mg/kg) 、稻壳空白及添加 (0.01mg/kg) 和稻秆空白及添加 (0.01mg/kg) 色谱图。

Figure 4. Chromatograms of 6-CBO

Chromatograms of 6-CBO (D-1~D-7, standard of 0.00167 mg/L, brown rice blank and spiked (0.01mg/kg)， paddy hull blank and spiked (0.01mg/kg)，rice straw blank and spiked (0.01mg/kg).

下载: 全尺寸图片幻灯片

图 2 HPFMPA色谱图

B-1~B-7分别为标样 (0.00167 mg/L) 、糙米空白及添加 (0.01 mg/kg) 、稻壳空白及添加 (0.01 mg/kg) 和稻秆空白及添加 (0.01 mg/kg) 色谱图。

Figure 2. Chromatograms of HPFMPA

Chromatograms of HPFMPA (B-1~B-7, standard of 0.00167 mg/L, brown rice blank and spiked (0.01 mg/kg)， paddy hull blank and spiked (0.01 mg/kg)，rice straw blank and spiked (0.01 mg/kg).

下载: 全尺寸图片幻灯片

图 3 HFMPA色谱图

C-1~C-7分别为标样 (0.00167 mg/L) 、糙米空白及添加 (0.01 mg/kg) 、稻壳空白及添加 (0.01 mg/kg) 和稻秆空白及添加 (0.01 mg/kg) 色谱图。

Figure 3. Chromatograms of HFMPA

Chromatograms of HFMPA (C-1~C-7, standard of 0.00167 mg/L, brown rice blank and spiked (0.01 mg/kg), paddy hull blank and spiked (0.01 mg/kg)，rice straw blank and spiked (0.01 mg/kg).

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表 1 噁唑酰草胺及其代谢产物质谱参数

Table 1. Mass spectrometric ( MS) parameters for detection of metamifop and its metabolites

化合物 Compound	保留时间 Retention time/min	离子化模式 Ionization mode	离子对 Ion pair, m/z	碰撞电压 Collision energy/ eV
噁唑酰草胺 metamifop	3.50	ESI⁺	441.1/180.1	27
噁唑酰草胺 metamifop	3.50	ESI⁺	441.1/288.1^*	23
HFMPA	1.64	ESI⁺	198/125.9^*	10
HFMPA	1.64	ESI⁺	198/180	10
HPFMPA	2.03	ESI⁺	290.1/180	10
HPFMPA	2.03	ESI⁺	290.1/180	10
6-CBO	2.26	ESI⁻	168/75.8	22
6-CBO	2.26	ESI⁻	168/131.8^*	18
注：^* 定量离子。Note: ^*Quantitative ion.

下载: 导出CSV

表 2 方法的正确度和精密度 (n=5)

Table 2. The trueness and precision of the method (n=5)

化合物 Compound	添加水平 Spiked level/ (mg/kg)	平均回收率 Average recovery/%			相对标准偏差 RSD/%
化合物 Compound	添加水平 Spiked level/ (mg/kg)	糙米 Brown rice	稻壳 Paddy hull	稻秆 Rice straw	糙米 Brown rice	稻壳 Paddy hull	稻秆 Rice straw
噁唑酰草胺 metamifop	0.01	91	80	96	9.0	2.6	10.8
	0.1	98	92	91	9.2	5.2	9.7
	2.0	98	79	103	0.9	1.7	3.3
HFMPA	0.01	94	88	100	4.9	2.1	8.3
	0.1	89	99	90	1.5	2.3	6.1
	2.0	92	84	103	4.5	2.6	6.6
HPFMPA	0.01	101	92	95	5.6	6.6	8.2
	0.1	100	108	97	2.8	9.8	6.6
	2.0	103	95	97	2.6	9.0	5.4
6-CBO	0.01	91	92	101	2.5	1.2	3.7
	0.1	85	98	94	3.0	2.1	5.1
	2.0	94	84	87	2.4	7.6	3.8

下载: 导出CSV

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