衍生化-气相色谱-三重四极杆质谱法同时测定粮食作物中三氯甲基吡啶及其代谢物残留

doi:10.3724/SP.J.1123.2019.11030

摘要/Abstract

摘要：

建立了粮食作物中三氯甲基吡啶及其代谢物6-氯吡啶甲酸的衍生化-气相色谱-三重四极杆质谱（GC-MS/MS）检测方法。选取高粱、小麦、玉米及爆谷等典型的粮食作物，采用酸性乙腈提取，以浓硫酸作为三氯甲基吡啶代谢物的衍生化试剂，优化了衍生化反应的最佳反应条件，并使用GC-MS/MS分析，以内标法对三氯甲基吡啶及其代谢物进行定量检测。结果表明，在0.025~0.4 mg/L范围内，线性关系良好，相关系数（r²）均大于0.995，在3个不同添加水平下的平均回收率在80.4%~98.4%之间，相对标准偏差（RSD）在1.0%~10.1%之间。该方法操作简单、高效，灵敏度高，抗干扰能力强，回收率和重复性良好，能够满足粮食作物中三氯甲基吡啶及其代谢产物残留量的检测要求。

关键词: 气相色谱-三重四极杆质谱, 三氯甲基吡啶, 6-氯吡啶甲酸, 粮食作物

Abstract:

A method based on precolumn derivatization along with gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS) was developed for the determination of nitrapyrin and its metabolite, 6-chloropicolinic acid, in crops. The samples were extracted by acid acetonitrile, and subjected to precolumn derivatization using a sulfoacid. The quantification of the analytes was performed by the internal standard method. Good linear relationships between the peak areas and mass concentrations of the analytes were obtained in the range of 0.025-0.2 mg/L with correlation coefficients greater than 0.995 (n=6). The limits of quantification (LOQs) were 0.05 mg/kg. The recoveries of the analytes in crops at three spiked levels (0.05, 0.1, and 0.2 mg/kg) were in the range of 80.4%-98.4%, with relative standard deviations between 1.0% and 10.1% (n=6). This new method satisfies the related regulations for the determination of nitrapyrin and its metabolite in crops.

Key words: gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS), nitrapyrin, 6-chloropicolinic acid, crops

孙灵慧, 陈捷, 徐娟, 李敏青, 陈文锐. 衍生化-气相色谱-三重四极杆质谱法同时测定粮食作物中三氯甲基吡啶及其代谢物残留[J]. 色谱, 2020, 38(6): 695-701.

SUN Linghui, CHEN Jie, XU Juan, LI Minqing, CHEN Wenrui. Simultaneous determination of nitrapyrin and its metabolite residues in food crops by derivatization with gas chromatography-triple quadrupole mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(6): 695-701.

图/表 9

表1 三氯甲基吡啶及其代谢产物的MRM参数

Table 1 MRM parameters of nitrapyrin and its metabolite

No.	Compound	Retention time/min	Quantitative ion pair (m/z)	Quantitative ion pair collision energy/V	Qualitative Ion pair (m/z)	Qualitative ion pair collision energy/V
* 6-Chloro-2-picolinic acid methyl ester is a derivative of the metabolite of nitrapyrin.
1	nitrapyrin	7.97	113/78	16	195.9/135	16
					195.9/195.9	5
2	6-chloro-2-picolinic acid methyl ester^*	7.32	193.9/133	16	112/76	10
					141/113	4
3	pyridine-2-carboxylic acid methyl ester	6.13	107.1/79	4	79.1/52	16
					78.1/51	10

图1 净化条件对三氯甲基吡啶及其代谢物回收率的影响

Fig. 1 Effects of purification conditions on the recoveries of nitrapyrin and its metabolite

图2 衍生时间对衍生物回收率的影响

Fig. 2 Effect of the derivatization time on the recovery of the derivative

图3 硫酸用量对衍生物响应值的影响

Fig. 3 Effect of the sulfuric acid amount on the response of the derivative

图4 采用不同色谱柱分离三氯甲基吡啶、6-氯-2-吡啶羧酸甲酯和2-吡啶甲酸甲酯的色谱图

Fig. 4 Chromatograms of nitrapyrin, 6-chloro-2-picolinic acid methyl ester, and pyridine-2-carboxylic acid methyl ester separated on different columns

表2 不同基质中三氯甲基吡啶及其代谢物的线性方程、相关系数、检出限和定量限

Table 2 Linear equations, correlation coefficients (r2), LODs, and LOQs of nitrapyrin and its metabolite in different matrices

Compound	Matrix	Linear equation	r²	LOD/(mg/kg)	LOQ/(mg/kg)
Y: peak area of product ion/peak area of internal standard×mass concentration of internal standard; X: mass concentration, g/L. Linear range: 0.025-0.4 mg/L.
Nitrapyrin	wheat	Y=2.20×10^-3X-1.57×10^-2	0.9953	0.01	0.05
	sorghum	Y=2.40×10^-3X+1.00×10^-3	0.9977
	maize	Y=2.50×10^-3+1.12×10^-2	0.9990
	popcorn	Y=2.50×10^-3X-6.50×10^-3	0.9988
6-Chloropicolinic acid	wheat	Y=5.60×10^-3X-2.21×10^-2	0.9999	0.001	0.05
	sorghum	Y=5.30×10^-3X+2.90×10^-3	0.9999
	maize	Y=2.90×10^-3X+5.50×10^-3	0.9995
	popcorn	Y=2.40×10^-3X+2.80×10^-3	0.9995

图5 三氯甲基吡啶、6-氯-2-吡啶羧酸甲酯和2-吡啶甲酸甲酯标准品的全扫描质谱图

Fig. 5 Full scan mass spectra of nitrapyrin, 6-chloro-2-picolinic acid methyl ester, and pyridine-2-carboxylic acid methyl ester standards

图6 三氯甲基吡啶、6-氯-2-吡啶羧酸甲酯和2-吡啶甲酸甲酯标准品的MRM色谱图

Fig. 6 MRM chromatograms of nitrapyrin, 6-chloro-2-picolinic acid methyl ester, and pyridine-2-carboxylic acid methyl ester standards

表3 不同基质中三氯甲基吡啶及其代谢物的加标回收率和精密度(n=6)

Table 3 Spiked recoveries and precisions of nitrapyrin and its metabolite in different matrices (n=6)

Compound	Added/(mg/kg)	Wheat		Sorghum		Maize		Popcorn
Compound	Added/(mg/kg)	Recovery/%	RSD/%	Recovery/%	RSD/%	Recovery/%	RSD/%	Recovery/%	RSD/%
Nitrapyrin	0.05	96.4	7.0	84.8	8.7	95.9	9.0	84.4	8.8
	0.1	84.1	2.1	83.1	1.4	89.0	6.5	89.2	8.2
	0.2	92.0	4.2	85.3	4.1	84.5	1.0	92.0	3.6
6-Chloropicolinic acid	0.05	80.4	3.4	88.7	10.1	98.4	2.4	86.7	8.0
	0.1	88.0	5.4	90.8	5.7	93.8	5.0	94.4	4.8
	0.2	90.0	1.8	91.1	2.6	87.4	4.4	83.9	1.9

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