超高效液相色谱-串联质谱法测定水稻中噁唑酰草胺残留量

doi:10.11924/j.issn.1000-6850.casb18120042

摘要/Abstract

摘要：

建立了检测水稻植株、稻壳、糙米、田水基质中噁唑酰草胺残留量的超高效液相色谱-串联质谱(UPLC-MS/MS)的分析方法。待测样品经乙腈匀浆提取、经PSA净化后,经ACQUITY UPLC BEH C₁₈色谱柱(50 mm×2.1 mm,1.7 μm)分离,以甲醇-水为流动相梯度洗脱,采用电喷雾电离串联质谱正离子多反应检测(MRM)模式测定,外标法定量。结果表明：噁唑酰草胺在0.001~0.05 μg/mL浓度范围内,在水稻植株、糙米、稻壳、田水基质中,供试农药的质量浓度与其相应的峰面积间呈良好线性相关,相关系数(r)分别为0.998、0.996、0.994和0.996;在0.005、0.05、0.5 mg/kg 3个水平下进行添加回收试验,噁唑酰草胺在水稻植株、稻壳、糙米、田水基质中的回收率分别在85.8%~114.6%、80.6%~106.4%、84.2%~95.0%和92.8%~109.3%之间,相对标准偏差(RSD)分别在2.7%~6.7%、3.8%~9.2%、2.9%~4.6%和5.0%~12.3%之间,定量限(LOQs)为0.005 mg/kg。该方法简单、快速、准确、灵敏,所得结果满足农药残留检测的要求,适用于水稻植株、糙米、稻壳、田水中噁唑酰草胺的残留检测。

关键词: 噁唑酰草胺, 超高效液相色谱-串联质谱, 水稻

Abstract:

An ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) method to detect metamifop residue in rice plant, rise husk, brown rice and rice field water was established, the samples were extracted with acetonitrile, and cleaned up by PSA, separated by ACQUITY UPLC BEH C₁₈ column (50 mm×2.1 mm, 1.7 μm) and gradient eluted with methanol-water, detected with multiple reaction monitoring (MRM) modes with electrospray ionization and then quantified with external standard method. The results showed that a good linear relationship in the range of 0.005-0.05 μg/mL was found of metamifop with rice plant, brown rice, rise husk and rice field water, with the correlation coefficients (r) of 0.998, 0.996, 0.994 and 0.996, respectively. The method was validated at three spike levels (0.005, 0.05 and 0.5 mg/kg), the average recoveries were 85.8%-114.6%, 80.6%-106.4%, 84.2%-95.0% and 92.8%-109.3% in rice plant, rise husk, brown rice and rice field water, with RSD of 2.7%-6.7%, 3.8%-9.2%, 2.9%-4.6% and 5.0%-12.3%, respectively. The limit of quantization (LOQs) was 0.005 mg/kg. This method could meet the determination requirements, and it was simple, quick, accurate and sensitive, could be used to study the residues of metamifop in rice.

Key words: metamifop, UPLC-MS/MS, rice

中图分类号:

张月. 超高效液相色谱-串联质谱法测定水稻中噁唑酰草胺残留量[J]. 中国农学通报, 2020, 36(9): 127-131.

Yue Zhang. Determination of Metamifop Residue in Rice by UPLC-MS/MS[J]. Chinese Agricultural Science Bulletin, 2020, 36(9): 127-131.

图/表 5

时间/ min	流速/ (mL/min）	流动相/%
时间/ min	流速/ (mL/min）	水	甲醇
0.0	0.25	90	10
0.1	0.25	90	10
2.0	0.25	10	90
3.0	0.25	10	90
3.1	0.25	90	10
5.0	0.25	90	10

表1. 梯度洗脱程序

化合物	保留时间/ min	定性、定量离子对 (Q1/Q3,m/z)	锥孔电压 DP/V	碰撞能量 CE/V
噁唑酰草胺	2.94	441/288^* 441/180	121	26 28

表2. 串联质谱监测模式下待测化合物的检测条件

基质	线性方程	相关系数 r	LOQ/ (mg/kg)	基质效应/ %ME
试剂	y=132938x+90	0.997	—	—
植株	y=8762913x+7071	0.998	0.005	65.9
糙米	y=38284316x-13604	0.996	0.005	288.0
稻壳	y=10950194x-7103	0.994	0.005	82.4
田水	y=40343151x-30022	0.996	0.005	303.5

表3. 噁唑酰草胺的线性方程、相关系数、定量限(LOQs)和基质效应

基质	添加水平/(mg/kg)	平均回收率/%	相对标准偏差RSD/%
植株	0.005	114.6	4.8
	0.05	114.3	2.7
	0.5	85.8	6.7
糙米	0.005	95.0	3.8
	0.05	92.3	3.9
	0.5	84.2	9.2
稻壳	0.005	106.4	4.6
	0.05	106.4	3.5
	0.5	80.6	2.9
田水	0.005	109.3	5.0
	0.05	102.1	6.6
	0.5	92.8	12.3

表4. 基质样品中的回收率和相对标准偏差(n=5)

图1. 多反应监测模式下噁唑酰草胺在水稻植株、糙米、稻壳和田水中标准品、空白样品及添加样品谱图 a 噁唑酰草胺在水稻植株的标准品(std 0.01 μg/mL)、空白样品和基质添加(0.05 mg/kg)样品的定量离子谱图 b 噁唑酰草胺在水稻糙米的标准品(std 0.01 μg/mL)、空白样品和基质添加(0.05 mg/kg)样品的定量离子谱图 c 噁唑酰草胺在水稻稻壳的标准品(std 0.01 μg/mL)、空白样品和基质添加(0.05 mg/kg)样品的定量离子谱图 d 噁唑酰草胺在水稻田水的标准品(std 0.01 μg/mL)、空白样品和基质添加(0.05 mg/kg)样品的定量离子谱图

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