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

doi:10.3724/SP.J.1123.2019.01051

Abstract

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

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.

Figures/Tables 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