A Modified QuEChERS Extraction and LC-MS/MS Method for the Determination of Pesticide Residues in Curry Leaves (Murraya koenigii)

Ranjith       Arimboor; Karunkara   Ramakrishna    Menon; Natarajan   Ramesh   Babu; Haneesh       Chandran

Abstract

Background: Increased consumer demand for curry leaves free from pesticides demands fast and reliable analytical methods for the analysis of pesticide residues.

Objective: The optimization of a QuEChERS based sample preparation technique with improved analytical accuracy by removing interfering matrix components for LC-MS/MS analysis of pesticide residues from curry leaves.

Methods: A modified QuEChERS solid phase extraction method was developed and validated for the analysis of 26 pesticides in fresh and dried curry leaves. The effects of the sample preparation steps and column retention time on the matrix suppression of analyte ions were also evaluated.

Results: Validation parameters were found within an acceptable range. The matrix effect evaluation studies showed that the QuEChERS sample preparation was able to minimize the ion suppression of analytes due to co-eluting matrix of components and that a d-SPE clean up step had major role in reducing matrix effect. The gradient mobile phase with longer retention time for analytes resulted in comparatively lesser matrix effects than the isocratic mobile phase of non-polar nature. Even after the clean up, a considerable number of compounds had more than 20% reduction in their MS response in the gradient mobile phase.

Conclusion: This study emphasized the need of proper sample clean up before a LC-MS/MS analysis and the usage of matrix matched standards and mobile phase that ultimately results in an appropriate analyte separation in reasonable retention times.

Keywords: Curry leaves, Murraya koenigii, pesticides, LC-MS/MS, matrix effect, QuEChERS.

[1] 
Kumar, V.S.; Sharma, A.; Tiwari, R.; Kumar, S. Murraya koenigii (Curry leaf): A review.  J  Med. Aromat. Plant Sci,  1999, 21, 1139-1141.
[2] 
Arulselvan, P.; Subramanian, S.P. Beneficial effects of Murraya koenigii leaves on antioxidant defense system and ultra structural changes of pancreatic cells in experimental diabetes in rats. Chem. Biol. Inter.,  2007, 165, 155-164.
[3] 
Khan, B.A.; Abraham, A.; Leelamma, S. Murraya koenigii and Brassica juncea alteration on lipid profile in 1-2 dimethyl hydrazine induced colon carcinogenesis. Invest. New Drugs,  1996, 14, 365-369.
[4] 
Nutan, M.T.H.; Hasnat, A.; Rashid, M.A. Anti bacterial and cytotoxic activities of Murraya koenigii. Fitoterapia,  1998, 69, 173-175.
[5] 
Ramsewak, R.S.; Nair, M.G. Strasburg, De Witt, D.L.; Nitidd, J.L. Biologically active carbazoles and alkaloids from Murraya koenigii. J. Agric. Food Chem.,  1999, 47, 444-447.
[6] 
Khan, B.A.; Abraham, A.; Leelamma, S. Biochemical response in rats to the addition of curry leaf (Muraraya koenigii) and mustard seed (Brassica juncea) to the diet. Plant Foods Hum. Nutr.,  1996, 49, 295-299.
[7] 
Luke, M.; Forberg, J.E.; Masumoto, H.T. Extraction and cleanup of organochlorine, organophosphate, organonitrogen & hydrocarbon pesticides in produce for determination by gas-liquid-chromatography. J. AOAC Int.,  1975, 58, 1020-1026.
[8] 
Hsu, R.C.; Biggs, I.; Saini, N.K. Solid-phase extraction cleanup of halogenated organic pesticides. J. Agric. Food Chem.,  1991, 39, 1658-1666.
[9] 
Adou, K.; Bontoyan, W.R.; Sweeney, P.J. Multi-residue method for the analysis of pesticide residues in fruits and vegetables by accelerated solvent extraction and capillary gas chromatography. J. Agric. Food Chem.,  2001, 49, 4153-4160.
[10] 
Barriada-Pereira, M.; Gonzalez-Castro, M.J.; Muniategui-Lorenzo, S.; Lopez-Mahia, P.; Prada-Rodriguez, D.; Fernandez-Fernandez, E. Determination of organochlorine pesticides in horticultural samples by microwave assisted extraction followed by GC-ECD. Int. J. Environ. Anal. Chem.,  2005, 85, 325-333.
[11] 
Valverde, G.A.; Fernandez Alba, A.R.; Contreras, M.; Aguera, A. Supercritical fluid extraction of pesticides from vegetables using anhydrous magnesium sulphate for sample preparation. J. Agric. Food Chem.,  1996, 44, 1780-1784.
[12] 
Stan, H.J. Pesticide residues analysis in foodstuffs applying capillary gas chromatography with mass spectrometric detection-state-of-the-art use of modified DFG-multimethod S19 and automated data evaluation. J. Chromatogr. A,  2000, 892, 347-377.
[13] 
Torres, C.M.; Pico, Y.; Manes, J. Analysis of pesticide residues in fruits and vegetables by matrix solid-phase dispersion (MSPD) and different gas chromatography elements-selective detector. Chromatograpia,  1995, 41, 685-692.
[14] 
Anastassiades, M.; Lehotay, M.; Stajnbaher, J.; Schenck, F.J. Fast and easy multi-residue employing acetonitrile extraction/partitioning and dispersive solid-phase extraction of pesticide residues in produce. J. AOAC Int.,  2003, 86, 412-413.
[15] 
Hou, X.; Han, M.; Da, H.; Yang, X.; Yi, S. A multi-residue method for the determination of 124 pesticides in rice by modified QuEChERS extraction and gas chromatography-tandem mass spectrometry. Food Chem.,  2013, 138, 1198-1205.
[16] 
Lehotay, S.J.; Son, K.A.; Kwon, H.; Koesukwiwat, U.; Fu, W.; Mastovska, K.; Hoh, E.; Leepipatpiboon, N. Comparison of QuEChERS sample preparation methods for the analysis of pesticide residue in fruits and vegetables. J. Chromatogr. A,  2010, 1217, 2548-2560.
[17] 
Mohapatra, S.; Manikrao, G.; Siddamallaiah, L.; Buddidhathi, R.; Mathada, N.Y. Analysis of 28 insecticides in curry leaves (Murraya koenigii L.) by gas chromatography and gas chromatography-mass spectrometry. Int. J. Environ. Anal. Chem.,  2017, 97, 14-28.
[18] 
Martínez-Domínguez, G.; Nieto-García, A.J.; Romero-González, R. Frenich. A.G. Application of QuEChERS based method for the determination of pesticides in nutraceutical products (Camellia sinensis) by liquid chromatography coupled to triple quadrupole tandem mass spectrometry. Food Chem.,  2015, 177, 182-190.
[19] 
Mol, H.G.J.; van Dam, R.C.J.; Steijger, O.M. Determination of polar organophosphorus pesticides in vegetables and fruits using liquid chromatography with tandem mass spectrometry, selection of extraction solvent. J. Chromatogr. A,  2003, 1015, 119-127.
[20] 
Kruve, A.; Kunnapas, A.; Herodes, K.; Leito, I. Matrix effects in pesticides multi-residue analysis by liquid chromatography-mass spectrometry. J. Chromatogr. A,  2008, 1187, 58-66.
[21] 
Lehotay, S.J.; de Kok, A.; Hiemstra, M.; van Bodegraven, P. Validation of a fast and easy method for the determination of residues from 229 pesticides in fruits and vegetables using gas and liquid chromatography and mass spectrometric detection. J. AOAC Int.,  2005, 88, 595-614.
[22] 
Document, No. SANCO/12495/2011 European Union 2011. Method validation and quality control procedures for pesticides residues analysis in food and feed. http://ec.Europa.eu/food/plant/protection/ pesticides/docs/qualcontrol_en.pdf
[23] 
Chambers, E.; Diane, M.; Wagrowsik, D.; Ziling, L.; Mazzeo, J.R. Systematic and comprehensive strategy for reducing matrix effects in LC/MS/MS analyses. J. Chromatogr. B 	,  2007, 852, 22-34.

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DOI https://dx.doi.org/10.2174/2213240606666181226143757	Print ISSN 2213-2406
Publisher Name Bentham Science Publisher	Online ISSN 2213-2414

Current Chromatography

A Modified QuEChERS Extraction and LC-MS/MS Method for the Determination of Pesticide Residues in Curry Leaves (Murraya koenigii)

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