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

doi:10.3724/SP.J.1123.2019.01051

色谱 ›› 2020, Vol. 38 ›› Issue (1): 120-126.DOI: 10.3724/SP.J.1123.2019.01051

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

陈正毅, 李运达, 张卓旻(), 李攻科()

中山大学化学学院, 广东广州 510275

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
张卓旻, Tel:(020)84110922, E-mail:zzm@mail.sysu.edu.cn;
基金资助:
国家自然科学基金(21675178);国家自然科学基金(21575167);国家自然科学基金(21976213);广东省公益研究与能力建设专项基金(2015A030401036);广州市科技计划项目(201604020165);广东省食品安全重点领域研发计划(2019B020211001)

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

CHEN Zhengyi, LI Yunda, ZHANG Zhuomin(), LI Gongke()

School of Chemistry, Sun Yat-sen University, Guangzhou 510275, China

Received:2019-01-30 Online:2020-01-08 Published:2020-12-11
Contact: ZHANG Zhuomin,LI Gongke
Supported by:
National Natural Science Foundation of China(21675178);National Natural Science Foundation of China(21575167);National Natural Science Foundation of China(21976213);Special Funds for Public Welfare Research and Capacity Building in Guangdong Province of China(2015A030401036);Guangzhou Sci-ence and Technology Program of China(201604020165);Research and Development Plan for Key Areas of Food Safety in Guangdong Province of China(2019B020211001)

摘要/Abstract

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。

关键词: 超高压液相色谱-串联质谱, 微热助吹扫捕集, 半挥发性农药残留, 蔬菜

Abstract:

A method for the analysis of 12 semi-volatile pesticide residues in vegetables was developed by miniaturized thermal-assisted purge-and-trap coupled with ultra high pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). Under the optimized conditions, the sample preparation could be completed within 10 min. The linear relationships of the 12 semi-volatile pesticide residues were good within their corresponding concentration ranges. The correlation coefficients were in range of 0.9918-0.9997. The limits of detection and limits of quantification were in range of 0.3-1.3 μg/kg and 1.0-4.3 μg/kg, respectively. The recoveries ranged from 80.0% to 120.0%, with intra-day and inter-day RSDs of less than 10%. This proposed method is quick and simple, and is suitable for the simultaneous and rapid analysis of semi-volatile pesticide residues in vegetables.

Key words: ultra high pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), miniaturized thermal-assisted purge-and-trap, semi-volatile pesticide residues, vegetable

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.

图/表 8

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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

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

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	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/%
Pesticide	Added/ (μg/kg)	Found/ (μg/kg)	Recovery/ %	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

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

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

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