Development and validation of modified QuEChERS method coupled with GC-MS/MS for 123 pesticide residues in food

Year 2018, Volume: 5 Issue: 2, 130 - 139, 05.07.2018

Şeyda Kıvrak , Mansur Harmandar

https://doi.org/10.21448/ijsm.408174

Cited By: 5

Abstract

In this study, a gas chromatography-tandem mass spectrometry (GC-MS/MS) instrument, which has been widely used in recent years and has high separation power, selectivity and ability to identify pesticides has been used. It is aimed that the main criterion of this analytical method, in which the QuEChERS methodology is used, is applicable to fast, easy, cheap, environmentally friendly and different matrices. At the same time with this method, 123 pesticide residues and their degradation products were quantitatively assayed by GC-MS/MS as well as method validations in tomatoe, lemon, lettuce, almonds, raisins, honey, green pepper, milk and flour. Tomatoe was selected as potential reference matrixes for the target. The steps of concentration and solvent exchange were performed in the resultant extracts for the purpose of improving analytical performance in terms of recovery, precision, linearity, of reducing the amount of co-extracts. Multiple reaction monitoring (MRM) was used to identify and quantify the pesticides. The samples were extracted with 1% acetic acid in acetonitrile, anhydrous magnesium acetate, anhydrous magnesium sulfate and clearing agent. For all pesticides, good linear calibrations with coefficients (R2) ≥0.99 for nearly all of the analytes were obtained. Limit of quantitation of most of the pesticides were in the range of 5-10 ng/g, and recovery of the method validation accuracy parameter was done at two different concentrations 10 ng/g and 50 ng/g were 88.6 - 99.7% and CV 1.60 – 14.0%.

Keywords

Pesticide, Chlorpyrifos, Deltamethrin, Validation, GC-MS/MS

Development and validation of modified QuEChERS method coupled with GC-MS/MS for 123 pesticide residues in food

Abstract

In
this study, a gas chromatography-tandem mass spectrometry (GC-MS/MS)
instrument, which has been widely used in recent years and has high separation
power, selectivity and ability to identify pesticides has been used. It is
aimed that the main criterion of this analytical method, in which the QuEChERS
methodology is used, is applicable to fast, easy, cheap, environmentally
friendly and different matrices. At the same time with this method, 123
pesticide residues and their degradation products were quantitatively assayed
by GC-MS/MS as well as method validations in tomatoe, lemon, lettuce, almonds,
raisins, honey, green pepper, milk and flour. Tomatoe was selected as potential
reference matrixes for the target. The steps of concentration and solvent
exchange were performed in the resultant extracts for the purpose of improving
analytical performance in terms of recovery, precision, linearity, of reducing
the amount of co-extracts. Multiple reaction monitoring (MRM) was used to
identify and quantify the pesticides. The samples were extracted with 1% acetic
acid in acetonitrile, anhydrous magnesium acetate, anhydrous magnesium sulfate
and clearing agent. For all pesticides, good linear calibrations with
coefficients (R2) ≥0.99 for nearly all of the analytes were obtained.  Limit of quantitation of most of the
pesticides were in the range of 5-10 ng/g, and recovery of the method
validation accuracy parameter was done at two different concentrations 10 ng/g
and 50 ng/g were 88.6 - 99.7% and CV 1.60 – 14.0%.

Keywords

Pesticide, Chlorpyrifos, Deltamethrin, Validation, GC-MS/MS

References

• [1] Nollet, L.M.L., Rathore, H.S. (2010). Handbook of pesticides: methods of pesticide residues analysis, NW/USA: Taylor & Francis, CRC press. [2] DG Health and Consumer Protection, September 2008, http://ec.europa.eu/food/plant/protection/pesticides/implementation_reg_396_2005.pdf, Accessed 29.01.18 [3] Martín-Plaza, L. (2005). Chromatographic-Mass Spectrometric Food Analysis for Trace determination of Pesticide Residues, Chapter 2, in Comprehensive Analytical Chemistry, ed: A.R. Fernández-Alba, The Netherlands: Elsevier. [4] Ahmed, F.E. (2001) Analyses of pesticides and their metabolites in foods and drinks. Trends in Analytical Chemistry, 20(11), 649–661. [5] Albero, B., Brunete, C.S., Tadeo, J.L. (2005). Multiresidue determination of pesticides in juice by solid-phase extraction and gas chromatography–mass spectrometry. Talanta, 66(4), 917–924. [6] Salquèbre, G., Schummer, C., Millet, M., Briand, O., Appenzeller, B.M.R. (2012). Multiclass pesticide analysis in human hair by gas chromatography tandem (triple quadrupole) mass spectrometry with solid phase microextraction and liquid injection. Analytica Chimica Acta, 710, 65-74. [7] Covaci, A., Hura, C., Gheorghe, A., Neels, H., Dirtu, A.C. (2008). Organochlorine contaminants in hair of adolescents from Iassy, Romania. Chemosphere, 72, 16-20. [8] Neuber, K., Merkel, G., Randow, F.F. (1999). Indoor air pollution by lindane and DDT indicated by head hair samples of children. Toxicology Letters, 107, 189-192. [9] Zhang, H., Chai, Z., Sun, H. (2007). Human hair as a potential biomonitor for assessing persistent organic pollutants. Environment International, 33, 685-693. [10] Duca, R.C., Salquebre, G., Hardy, E., Appenzeller, B.M.R. (2014). Comparison of solid phase- and liquid/liquid-extraction for the purification of hair extract prior to multi-class pesticides analysis. Journal of chromatography B, Analytical Technologies in The Biomedical and Life Sciences, 955-956. [11] Gill, U., Covaci, A., Ryan, J.J., Emond, A. (2004). Determination of persistent organohalogenated pollutants in human hair reference material (BCR 397): an interlaboratory study. Analytical and Bioanalytical Chemistry, 380, 924-929. [12] Wielgomas, B., Czarnowski, W., Jansen, E.H.J.M. (2012). Persistent organochlorine contaminants in hair samples of Northern Poland population, 1968-2009. Chemosphere, 89, 975-981. [13] Lehmann, E., Oltramare, C., de Alencastro, L.F. (2018). Development of a modified QuEChERS method for multi-class pesticide analysis in human hair by GC-MS and UPLC-MS/MS. Analytica Chimica Acta, 999, 87-98. [14] Jesús, F., Hladki, R., Gérez, N., Besil, N., Niell, S., Fernández, G., Heinzen, H., Cesio, M.V. (2018). Miniaturized QuEChERS based methodology for multiresidue determination of pesticides in odonate nymphs as ecosystem biomonitors. Talanta, 178, 410–418. [15] Anastassiades, M., Lehotay, S.J., Stajnbaher, D., Schenck, F.J. (2003). Fast and Easy Multiresidue Method Employing Acetonitrile Extraction/Partitioning and “Dispersive Solid-Phase Extraction” for the Determination of Pesticide Residues in Produce. The Journal of AOAC International, 8(6), 412. [16] Lehotay, S. J., Son, K. A., Kwon, H., Koesukwiwat, U., Fu, W., Mastovska, K., Hoh, E., Leepipatpiboon, N. (2010). Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. Journal of Chromatography A, 1217, 2548–2560. [17] Słowik-Borowiec, M. (2015). Validation of a QuEChERS-Based Gas Chromatographic Method for Multiresidue Pesticide Analysis in Fresh Peppermint Including Studies of Matrix Effects. Food Anayitical Methods, 8, 1413-1424. [18] Chen, H., Yin, P., Wang, Q., Jiang, Y., Liu, X. (2014). A Modified QuEChERS Sample Preparation Method for the Analysis of 70 Pesticide Residues in Tea Using Gas Chromatography-Tandem Mass Spectrometry. Food Anayitical Methods, 7, 1577–1587. [19] Mastovska, K., Lehotay, S.J. (2004). Evaluation of common organic solvents for gas chromatographic analysis and stability of multiclass pesticide residues. Journal of Chromatography A, 1040(2), 259–272.
• Niessen, W.M.A., Manini, P., & Andreoli, R. (2006). Matrix effects in quantitative pesticide analysis using liquid chromatography-mass spectrometry. Mass Spectrometry Reviews, 25, 881-899.
• Ferrer, C., Malato, O., Agüera, A., & Fernandez-Alba, A. R. (2012). Application of HPLC–TOF MS and HPLC–QTOF-MS/MS for Pesticide Residues Analysis in Fruit and Vegetable Matrices, 1-60, in Comprehensive Analytical Chemistry, (ed:) Farré M., Barceló D MA-USA, Elsevier, 428.
• Armbruster, D.A., Pry, T. (2008). Limit of Blank, Limit of Detection and Limit of Quantitation. The Clinical Biochemist Reviews, 29 Suppl (i), 49-52.
• CEC (2008) Implementation of Regulation (EC) No 396/2005 on Maximum Residues Levels of pesticides. https://eur-lex.europa.eu/legal-ontent/EN/ALL/?uri=CELEX%3A32005R0396. pdf, Accessed 29.01.18