Development and validation of a method to determine pesticides in river water using QuEChERS combined with UHPLC-MS/MS

The continuous increase in the use and release of pesticides is worrisome because water contamination can affect health and the environment. This study optimized and validated a multi-residue method in water. The method was developed using the QuEChERS method (Quick, Easy, Cheap, Effective, Rugged, and Safe) followed by ultrahigh- performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). The validation was performed on the matrix (river water) regarding accuracy, precision, linearity, limits of detection (LODs) and limits of quantification (LOQs). LODs were below 3.03 µg L^-1and LOQs were from 6.25 to 9.18 µg L^-1. The accuracy (recoveries in the range of 80-117%) and for Inter-day precision, the coefficients of variation ranged from 0.35 to 15.71%, and for Intra-day precision were in the range of 0.48 to 7.02%.

Keywords:
multi-residue analysis; pesticide; QuEChERS; water

Authorship

Vanessa Carvalho Pereira Ramos ^**Corresponding author: Vanessa Carvalho Pereira Ramos, e-mail: vanessa.carvalho2005@gmail.com

Departamento de Química. Universidade Estadual do Centro-Oeste (UNICENTRO), Rua Simeão Varela de Sá, n° 3, CEP: 85040-080, Guarapuava, PR, Brazil. E-mail: vanessa.carvalho2005@gmail.com, spquinaia@gmail.com, yohandra@unicentro.br, chrischineider@outlook.comUniversidade Estadual do Centro-OesteBrazilGuarapuava, PR, BrazilDepartamento de Química. Universidade Estadual do Centro-Oeste (UNICENTRO), Rua Simeão Varela de Sá, n° 3, CEP: 85040-080, Guarapuava, PR, Brazil. E-mail: vanessa.carvalho2005@gmail.com, spquinaia@gmail.com, yohandra@unicentro.br, chrischineider@outlook.com

https://orcid.org/0000-0002-1478-7647

Sueli Pércio Quináia

https://orcid.org/0000-0002-1485-1063

Yohandra Reyes Torres

https://orcid.org/0000-0003-1566-0223

Liliane Schier de Lima

Alphacarbo Industrial LTDA, Estrada Municipal Benedito de Paula Louro, s/n, BR-277, km 342, CEP: 84100-970, Guarapuava, PR, Brazil. E-mail: liliane@alphacarbo.com.brAlphacarbo Industrial LTDABrazilGuarapuava, PR, BrazilAlphacarbo Industrial LTDA, Estrada Municipal Benedito de Paula Louro, s/n, BR-277, km 342, CEP: 84100-970, Guarapuava, PR, Brazil. E-mail: liliane@alphacarbo.com.br

https://orcid.org/0000-0002-7759-5423

Christiane Schineider Machado

https://orcid.org/0000-0003-1619-8667

^*Corresponding author: Vanessa Carvalho Pereira Ramos, e-mail: vanessa.carvalho2005@gmail.com

SCIMAGO INSTITUTIONS RANKINGS

Figures | Tables

Figures (1)
Tables (4)

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Figure 1.
Selectivity of pesticides (30 µg L^-1) in (A) ACN and (B) in natural water SRM mode.

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Table 1.
Mass spectrometric parameters for each pesticide.

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Table 2.
Linear regression of pesticide analytical curves in natural water by UHPLC-MS/MS.

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Table 3.
Results of precision and accuracy for the determination of pesticides in natural water by UHPLC-MS/MS.

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Table 4.
Comparative results from the literature.

Figure 1. Selectivity of pesticides (30 µg L^-1) in (A) ACN and (B) in natural water SRM mode.

Table 1. Mass spectrometric parameters for each pesticide.

Pesticide	Chemical structure	Rt (min)	Cone (v)	MRM transition	CE (eV)
Imidacloprid		2.00	36	255.99>175.10 255.99 >209.06*	14/14
Atrazine		3.98	40	216.10>174.10* 216.10 > 95.93	18*/22
Diflubenzuron		5.28	20	311.00>158.00* 311.00> 141.00	15*/30
Pyraclostrobin		6.21	32	388.07>194.02* 388.07 > 163.02	12*/31
Methomyl		1.53	15	163.21 > 87.90* 163.21 > 105.90	10/10

The asterisk * in the MRM transition indicates the quantifier ion.
CE: Collision Energy.
MRM: Multiple reaction monitoring.

Table 2. Linear regression of pesticide analytical curves in natural water by UHPLC-MS/MS.

Calibration Equation		Parameters
		R²	F_(reg.)	p	F_lack-of-fit	F_{critical value}	p
Atrazine	$y = 43899485 + 173465 x$	0.995	4562.48	0.00	2.52	2.74	0.065
Imidacloprid	$y = 1856709 + 150242 x$	0.988	1826.02	0.00	2.21	2.77	0.098
Diflubenzuron	$y = 3595875 + 351046 x$	0.971	781.26	0.00	0.70	2.77	0.628
Pyraclostrobin	$y = 23517408 + 992234 x$	0.993	3272.70	0.00	1.21	2.74	0.343
Methomyl	$y = 3266270 + 464954 x$	0.994	3130.55	0.00	1.71	3.03	0.202

Table 3. Results of precision and accuracy for the determination of pesticides in natural water by UHPLC-MS/MS.

Pesticide	Concentration (µg L^-1)	Intra-day precision (% RSD)	Inter-day precision (% RSD)	Accuracy (%)
Atrazine	30	7.02	6.22	97.0
	50	3.35	12.29	98.3
	100	1.07	12.24	96.8
Imidacloprid	30	4.73	1.94	80.0
	50	2.96	5.95	117.2
	100	1.05	6.30	109.6
Diflubenzuron	30	3.88	15.71	91.5
	50	5.76	10.39	99.8
	100	4.35	8.14	96.0
Pyraclostrobin	30	2.39	2.82	93.9
	50	3.12	6.53	100.5
	100	3.07	6.00	97.5
Methomyl	30	3.75	0.35	103.4
	50	1.47	4.86	113.1
	100	0.48	4.22	103.9

Table 4. Comparative results from the literature.

Analytes	Sample	Method	LOD - LOQ	Ref
Methomyl Other pesticides (48)	Surface water	DI-SPME GC-ITMS/MS	1.09 - 1.43 µg L^-1 0.001-0.458 µg L^-1 0.04-1.43 µg L^-1	Jabaliet al.(2019)JABALI, Y.; MILLET, M.; EL-HOZ, M. Optimization of a DI-SPME-GC-MS/MS method for multi-residue analysis of pesticides in waters. Microchemical Journal, v. 147, p. 83-92, 2019. https://doi.org/10.1016/j.microc.2019.03.004 https://doi.org/10.1016/j.microc.2019.03...
Imidacloprid	Water bodies of agricultural	HPLC/DAD	0.15 - 0.7 µg mL^-1	Hrybovaet al.(2019)HRYBOVA, N. Y.; KHYZHAN, O. I.; MAKSIN, V. I.; KAVSHUN, L. O.; TANKHA, O. L. Determination of xenobiotic imidacloprid content in surface waters. Journal of Water Chemistry and Technology, v. 41, p. 313-317, 2019. https://doi.org/10.3103/S1063455X19050072 https://doi.org/10.3103/S1063455X1905007...
Pesticides (55)	Agricultural water	QuEChERS LC-MS/MS	0.02 - 3.0 µg L^-1 0.1 - 9.9 µg L^-1	Songet al.(2020)SONG, N. E.; JUNG, Y. S.; CHOI, J. Y.; KOO, M.; CHOI, H. K.; SEO, D. H. et al. Development and application of a multi-residue method to determine pesticides in agricultural water using QuEChERS extraction and LC-MS/MS analysis. Separations, v. 7, n. 4, p. 52, 2020. https://doi.org/10.3390/separations7040052 https://doi.org/10.3390/separations70400...
Hormones, endocrine, disruptor, pesticides	Tap water and wastewater sample	DLLME GC-MS	0.09 - 3.36 ng mL^-1 0.31 - 11.19 ng mL^-1	Chormeyet al.(2017)CHORMEY, D. S.; BÜYÜKPINAR, Ç.; TURAK, F.; KOMESLI, O. T.; BAKIRDERE, S. Simultaneous determination of selected hormones, endocrine disruptor compounds, and pesticides in water medium at trace levels by GC-MS after dispersive liquid-liquid microextraction. Environmental monitoring and assessment, v. 189, p. 1-10, 2017. https://doi.org/10.1007/s10661-017-6003-6 https://doi.org/10.1007/s10661-017-6003-...
Pesticides (8)	River and well water samples.	QuEChERS GC-MS	0.3- 4 µg L^-1 0.95- 13.69 µg L^-1	Abdel Ghani and Hanafi (2016)
Pesticides (30)	Drainage water	QuEChERS GC-MS	(LOQ) 4.59 - 15.91 ng mL^-1	Salamaet al.(2022)SALAMA, G.; EL GINDY, A.; ABDEL HAMEED, Eman A. The use of experimental design for optimisation of QuEChERS extraction of commonly used pesticides in Egyptian soil and drainage water and their determination by GC/MS. International Journal of Environmental Analytical Chemistry, v. 102, n. 16, p. 4238-4249, 2022. https://doi.org/10.1080/03067319.2020.1781837 https://doi.org/10.1080/03067319.2020.17...

DI-SPME: Direct immersion solid-phase micro-extraction
GC-ITMS/MS: Gas chromatography-ion trap tandem mass spectrometry
HPLC/DAD: High-performance liquid chromatography with a spectrophotometric (diode array detector) detector
GC-MS: Gas chromatography-mass spectrometry.

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Instituto de Pesquisas Ambientais em Bacias Hidrográficas Instituto de Pesquisas Ambientais em Bacias Hidrográficas (IPABHi), Estrada Mun. Dr. José Luis Cembranelli, 5000, Taubaté, SP, Brasil, CEP 12081-010 - Taubaté - SP - Brazil
E-mail: ambi.agua@gmail.com

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Development and validation of a method to determine pesticides in river water using QuEChERS combined with UHPLC-MS/MS

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[1] ^*Corresponding author: Vanessa Carvalho Pereira Ramos, e-mail: vanessa.carvalho2005@gmail.com