Determination of 18 pesticide residues in environmental water by solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry

doi:10.3724/SP.J.1123.2019.12022

Abstract

Abstract:

A method was developed for the simultaneous determination of 18 pesticide residues in environmental water by solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry (SPE-UPLC-MS/MS). The samples were purified and enriched by a large-volume SPE apparatus through a Cleanrt^®-PEP SPE column at a rate of 2 mL/min. After being concentrated 50-fold, the samples were detected by UPLC-MS/MS and quantified by the external standard method. The target compounds showed good linearity in the range of 0.5-50 μg/L, with linear correlation coefficients (R²) ≥0.995. At spiked levels of 10, 100 and 1000 ng/L, the average recoveries of the 18 pesticides in the three different environmental water samples were 71.3%-105.9%, and the relative standard deviations (RSDs, n=5) were 1.3%-9.9%. LOQs of the 18 pesticides were 10 ng/L. The method was applied to the detection of the water environment around Tai'an City, and no pesticide residues were detected at any of the collection sites. The method has the advantages of good purification effect, high versatility, sensitivity, and accuracy, and operational simplicity. The method is suitable for the determination of the 18 pesticides in environmental water.

Key words: ultra performance liquid chromatography-tandem mass spectrometry(UPLC-MS/MS), solid phase extraction (SPE), pesticide, environmental water

YANG Song, ZOU Nan, GAO Yun, XU Leyuan, ZHANG Wenwen, PAN Canping, MU Wei. Determination of 18 pesticide residues in environmental water by solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(7): 826-832.

Figures/Tables 6

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Pesticide	Retention time/min	Monitoring ion pair (m/z)	Cone voltage/V	Collision energy/V
* Quantitative ion pair.
Pyrimethanil	2.10	200.00/82.00	25	24
		200.00/107.00^*		24
Acetamiprid	1.40	223.00/56.10	30	15
		223.00/126.00^*		20
Dimethoate	1.42	230.10/125.00^*	5	10
		230.10/199.00		20
Clothianidin	1.32	250.00/132.00	25	15
		250.00/169.00^*		10
Imidacloprid	1.28	256.10/175.10	25	20
		256.10/209.10^*		15
Metalaxyl	2.08	280.10/192.10	10	20
		280.10/220.10^*		15
Thiamethoxam	1.12	292.00/132.00	25	20
		292.00/211.20^*		10
Pyriproxyfen	3.06	322.10/96.00^*	5	15
		322.10/277.10		10
Propiconazole	2.68	342.00/69.00^*	15	20
		342.00/159.00		25
Chlorpyrifos	3.12	349.90/198.00^*	27	20
		349.90/97.00		32
Etoxazole	3.16	360.20/141.10^*	60	25
		360.20/57.20		25
Carbosulfan	3.53	381.00/118.00^*	40	22
		381.00/76.00		34
Diafenthiuron	3.23	385.20/329.16^*	30	18
		385.20/278.20		30
Pyraclostrobin	2.69	388.10/193.90^*	5	12
		388.10/163.00		25
Etofenprox	3.61	394.30/106.90^*	26	43
		394.30/177.00		15
Spirodiclofen	3.24	411.14/71.16^*	35	15
		411.14/313.10		1
Bifenthrin	3.65	440.30/166.10	25	39
		440.30/181.10^*		11
Thifluzamide	2.51	528.70/148.00^*	25	36
		528.70/168.00		25

Pesticide	Retention time/min	Monitoring ion pair (m/z)	Cone voltage/V	Collision energy/V
* Quantitative ion pair.
Pyrimethanil	2.10	200.00/82.00	25	24
		200.00/107.00^*		24
Acetamiprid	1.40	223.00/56.10	30	15
		223.00/126.00^*		20
Dimethoate	1.42	230.10/125.00^*	5	10
		230.10/199.00		20
Clothianidin	1.32	250.00/132.00	25	15
		250.00/169.00^*		10
Imidacloprid	1.28	256.10/175.10	25	20
		256.10/209.10^*		15
Metalaxyl	2.08	280.10/192.10	10	20
		280.10/220.10^*		15
Thiamethoxam	1.12	292.00/132.00	25	20
		292.00/211.20^*		10
Pyriproxyfen	3.06	322.10/96.00^*	5	15
		322.10/277.10		10
Propiconazole	2.68	342.00/69.00^*	15	20
		342.00/159.00		25
Chlorpyrifos	3.12	349.90/198.00^*	27	20
		349.90/97.00		32
Etoxazole	3.16	360.20/141.10^*	60	25
		360.20/57.20		25
Carbosulfan	3.53	381.00/118.00^*	40	22
		381.00/76.00		34
Diafenthiuron	3.23	385.20/329.16^*	30	18
		385.20/278.20		30
Pyraclostrobin	2.69	388.10/193.90^*	5	12
		388.10/163.00		25
Etofenprox	3.61	394.30/106.90^*	26	43
		394.30/177.00		15
Spirodiclofen	3.24	411.14/71.16^*	35	15
		411.14/313.10		1
Bifenthrin	3.65	440.30/166.10	25	39
		440.30/181.10^*		11
Thifluzamide	2.51	528.70/148.00^*	25	36
		528.70/168.00		25

Pesticide	Matrix	10 ng/L		100 ng/L		1000 ng/L
Pesticide	Matrix	Recovery/%	RSD/%	Recovery/%	RSD/%	Recovery/%	RSD/%
Pyrimethanil	surface water	79.9	4.8	88.7	3.3	102.1	5.4
	chemical sewage	81.2	5.1	87.9	2.9	97.2	1.9
Acetamiprid	surface water	89.3	6.1	103.2	1.7	87.	6.3
	chemical sewage	99.4	2.8	99.1	3.6	102.4	2.5
Dimethoate	surface water	77.8	4.6	88.9	2.8	92.2	1.9
	chemical sewage	84.2	2.9	101.3	3.1	89.6	2.8
Clothianidin	surface water	97.6	3.1	95.8	7.2	92.9	2.3
	chemical sewage	92.8	2.9	99.7	6.1	84.7	5.6
Imidacloprid	surface water	93.5	5.4	103.2	9.9	85.7	5.7
	chemical sewage	83.9	6.2	81.0	1.6	88.1	5.1
Metalaxyl	surface water	87.3	4.4	84.8	3.2	90.4	6.1
	chemical sewage	92.7	6.1	72.8	1.9	97.8	2.8
Thiamethoxam	surface water	91.3	1.9	90.3	7.2	75.2	4.6
	chemical sewage	91.4	6.3	81.3	8.1	71.3	2.9
Pyriproxyfen	surface water	84.3	2.5	76.5	6.5	78.8	3.1
	chemical sewage	78.3	1.9	79.5	2.9	90.3	2.9
Propiconazole	surface water	81.5	2.8	87.3	2.4	82.9	5.4
	chemical sewage	89.2	3.8	77.7	8.0	82.3	6.2
Chlorpyrifos	surface water	104.2	3.2	82.4	8.1	85.5	4.4
	chemical sewage	105.9	1.8	85.0	6.5	81.3	6.1
Etoxazole	surface water	103.3	4.2	82.3	2.9	78.1	8.4
	chemical sewage	91.2	1.7	85.5	1.7	80.1	6.2
Carbosulfan	surface water	98.9	3.6	81.3	3.6	92.2	4.4
	chemical sewage	92.8	2.8	78.1	2.8	85.5	6.1
Diafenthiuron	surface water	89.7	3.1	80.1	3.1	77.6	1.9
	chemical sewage	92.8	7.2	92.2	7.2	80.2	6.3
Pyraclostrobin	surface water	95.3	8.1	85.5	6.1	82.0	2.5
	chemical sewage	85.4	6.5	78.6	2.9	71.5	1.9
Etofenprox	surface water	79.5	2.9	82.8	7.2	74.9	2.8
	chemical sewage	98.8	1.7	87.2	8.1	86.3	2.8
Spirodiclofen	surface water	104.1	3.6	74.9	6.5	82.1	3.1
	chemical sewage	103.4	2.8	86.3	2.9	92.5	7.2
Bifenthrin	surface water	92.3	1.9	82.1	1.7	83.8	6.1
	chemical sewage	84.1	1.7	92.5	3.6	76.2	2.9
Thifluzamide	surface water	77.6	1.3	83.8	2.8	80.3	7.2
	chemical sewage	79.2	2.1	76.2	2.4	82.6	8.2

Pesticide	Matrix	10 ng/L		100 ng/L		1000 ng/L
Pesticide	Matrix	Recovery/%	RSD/%	Recovery/%	RSD/%	Recovery/%	RSD/%
Pyrimethanil	surface water	79.9	4.8	88.7	3.3	102.1	5.4
	chemical sewage	81.2	5.1	87.9	2.9	97.2	1.9
Acetamiprid	surface water	89.3	6.1	103.2	1.7	87.	6.3
	chemical sewage	99.4	2.8	99.1	3.6	102.4	2.5
Dimethoate	surface water	77.8	4.6	88.9	2.8	92.2	1.9
	chemical sewage	84.2	2.9	101.3	3.1	89.6	2.8
Clothianidin	surface water	97.6	3.1	95.8	7.2	92.9	2.3
	chemical sewage	92.8	2.9	99.7	6.1	84.7	5.6
Imidacloprid	surface water	93.5	5.4	103.2	9.9	85.7	5.7
	chemical sewage	83.9	6.2	81.0	1.6	88.1	5.1
Metalaxyl	surface water	87.3	4.4	84.8	3.2	90.4	6.1
	chemical sewage	92.7	6.1	72.8	1.9	97.8	2.8
Thiamethoxam	surface water	91.3	1.9	90.3	7.2	75.2	4.6
	chemical sewage	91.4	6.3	81.3	8.1	71.3	2.9
Pyriproxyfen	surface water	84.3	2.5	76.5	6.5	78.8	3.1
	chemical sewage	78.3	1.9	79.5	2.9	90.3	2.9
Propiconazole	surface water	81.5	2.8	87.3	2.4	82.9	5.4
	chemical sewage	89.2	3.8	77.7	8.0	82.3	6.2
Chlorpyrifos	surface water	104.2	3.2	82.4	8.1	85.5	4.4
	chemical sewage	105.9	1.8	85.0	6.5	81.3	6.1
Etoxazole	surface water	103.3	4.2	82.3	2.9	78.1	8.4
	chemical sewage	91.2	1.7	85.5	1.7	80.1	6.2
Carbosulfan	surface water	98.9	3.6	81.3	3.6	92.2	4.4
	chemical sewage	92.8	2.8	78.1	2.8	85.5	6.1
Diafenthiuron	surface water	89.7	3.1	80.1	3.1	77.6	1.9
	chemical sewage	92.8	7.2	92.2	7.2	80.2	6.3
Pyraclostrobin	surface water	95.3	8.1	85.5	6.1	82.0	2.5
	chemical sewage	85.4	6.5	78.6	2.9	71.5	1.9
Etofenprox	surface water	79.5	2.9	82.8	7.2	74.9	2.8
	chemical sewage	98.8	1.7	87.2	8.1	86.3	2.8
Spirodiclofen	surface water	104.1	3.6	74.9	6.5	82.1	3.1
	chemical sewage	103.4	2.8	86.3	2.9	92.5	7.2
Bifenthrin	surface water	92.3	1.9	82.1	1.7	83.8	6.1
	chemical sewage	84.1	1.7	92.5	3.6	76.2	2.9
Thifluzamide	surface water	77.6	1.3	83.8	2.8	80.3	7.2
	chemical sewage	79.2	2.1	76.2	2.4	82.6	8.2

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