DEVELOPMENT AND VALIDATION OF THE METHOD FOR CO-DETERMINATION OF PESTICIDE RESIDUES IN WINTER WHEAT GRAIN BY GAS CHROMATOGRAPHY WITH MASS SPECTROMETRIC DETECTION
Abstract
Method for determination of 69 pesticides from different classes (amides, anilinopyrimidines, dinitroanilines, imidazoles, carbamates, carbanilates, morpholines, neonicotinoids, organodithiophosphates, organothiophosphates, pyrethroids, simmtriazines, esters, strobilurins, thiocarbamates, triazoles, etc.) in winter wheat grain by gas chromatography with mass spectrometric detection has been developed and validated by experimental data. The developed extraction method of sample preparation is simple, quick, consumes only cheap and rather common reagents and provides extracts clean enough to obtain reproducible quantitative results without cleaning of injector liner at least for 200 injections. The recovery values of studied pesticides from winter wheat grain were between 76 and 118 % with RSD values below 9 % at 10.0, 20.0 and 200 µg·kg–1 spiking levels. Detection limits were less or equal to 0.01 mg·kg−1 for all the studied pesticides. The obtained limits of quantification were below or equal to the maximum residue levels (MRLs) which are set by Belarus and the European Union for the corresponding pesticides in cereal grains. The linear range used in the calibration curves was from 50 to 3000 µg·L–1 with the values of the determination coefficients R2 more than 0.997. The developed method was successfully used for the analysis of cereal grains for the residues of the pesticides, which were under registration trials held in Belarus in 2015.
About the Author
M. F. ZayatsBelarus
Ph.D. (analytical chemistry), Leading Scientist of the Pesticide Dynamics Laboratory
References
1. Pleshko L. V., Khvalei O. A., Gololob T. I., Apanovich A. Iu., Boiarchuk V. E., Pesterev S. A., Gosudarstvennyi reestr sredstv zashchity rastenii (pestitsidov) i udobrenii, razreshennykh k primeneniiu na territorii Respubliki Belarus’: spravochnoe izdanie [State Register of plant protection products (pesticides) and fretilizeds allowed for use in the Republic of Belarus: a reference book], Minsk, BY, 2014.
2. “Resolution of the Ministry of Health of the Republic of Belarus No. 149 of 27.09.2012 “On the Approval of Sanitary Norms and Regulations” Requirements for the Application, Conditions of Transport and Storage of Pesticides (Plant Protection Products), Agrochemicals and Mineral Fertilizers”, Hygienic Standard “Hygienic Norms for the Content of Active Substances of Pesticides ( Plant protection products) in environmental objects, food raw materials, foodstuffs” and the recognition of some Resolution of the Chief Sanitary Doctor the Republic of Belarus and their individual structural elements””, Natsional’nyi reestr pravovykh aktov Respubliki Belarus’ [National Register of Legal Acts of the Republic of Belarus], 2012, no. 8/26455.
3. “EU Pesticides Database. Search pesticide residues”, available at: http://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/public/?event=pesticide.residue.selection&language=EN, (Accessed 07.07.2016).
4. MUK 4.1.2054-06. Metodicheskie ukazaniia po opredeleniiu ostatochnykh kolichestv prokhloraza v vode, pochve, zerne i solome zernovykh kolosovykh kul’tur metodom vysokoeffektivnoi zhidkostnoi khromatografii: utv. Rospotrebnadzorom 10.04.2006 [Methodical instructions for determining the residual amounts of prochloraz in water, soil, grain and straw of cereal crops using the method of high-performance liquid chromatography: approved by Rospotrebnadzor on 10.04.2006], “Russ. State. Agrarian University - MAAA named after K.A. Timiryazev. Educational and scientific consulting center “Agroecology of pesticides and agrochemicals”, Moscow, RU, 2006.
5. MUK 4.1.2068-06. Metodicheskie ukazaniia po opredeleniiu ostatochnykh kolichestv pendimetalina v zerne zernovykh kolosovykh kul’tur, risa, kukuruzy, rastitel’nykh maslakh, zelenoi masse kukuruzy, risovoi solomke metodom gazozhidkostnoi khromatografii : utv. Rospotrebnadzorom 05.05.2006 [Methodical guidelines for the determination of residual amounts of pendimethalin in grain cereal crops, rice, maize, vegetable oils, green maize, rice straws by gas liquid chromatography: approved by Rospotrebnadzor on 05.05.2006], “Federal scientific center of hygiene named after F.F. Erisman”, Mytischi, RU, 2006.
6. MUK 4.1.1228-03. Opredelenie ostatochnykh kolichestv spiroksamina v vode, pochve, zerne, zelenoi masse i solome zlakovykh kul’tur, vinograde metodom gazozhidkostnoi khromatografii. Metodicheskie ukazaniia : utv. Glavnym gosudarstvennym sanitarnym vrachom RF 16.03.2003 [Determination of spiroхamine residual amounts in water, soil, grain, green mass and straw of cereals, grapes by gas-liquid chromatography. Methodical instructions: approved by Chief State Sanitary Doctor of the Russian Federation 16.03.2003], St. Petersburg Scientific Research. Institute of Forestry; All-Russ. Scientific Research Institute of Plant Protection, St. Petersburg, RU, 2003.
7. MUK 4.1.2903-11. Opredelenie ostatochnykh kolichestv biksafena v vode, pochve, zerne i solome zernovykh kul’tur metodom vysokoeffektivnoi zhidkostnoi khromatografii. Metodicheskie ukazaniia : utv. Rospotrebnadzorom 12.07.2011 [Determination of bixapten residual amounts in water, soil, grain and straw of cereal crops by high-performance liquid chromatography. Methodical instructions: approved by Rospotrebnadzor 12/07/2011], “Russ. State Agrarian University - MAAA named after K.A. Timiryazev. Educational and scientific consulting center “Agroecology of pesticides and agrochemicals”, Moscow, RU, 2011.
8. MUK 4.1.1966-05. Opredelenie ostatochnykh kolichestv protiokonazola po ego osnovnomu metabolitu protiokonazol-destio v zerne i solome zernovykh kolosovykh kul’tur metodom gazozhidkostnoi khromatografii. Metodicheskie ukazaniia : utv. Rospotrebnadzorom 21.04.2005 [Determination of prothioconazole residual amounts by its main metabolite, prothioconazole-desthio in grain and straw of cereal crops, by gas-liquid chromatography. Methodical instructions: approved by Rospotrebnadzor on 21.04.2005], All-Russian Research Institute of Phytopathology, The Great Vyazemy, RU, 2005.
9. MUK 4.1.2172-07. Opredelenie ostatochnykh kolichestv tau-fluvalinata v zerne i solome zernovykh kul’tur, v iagodakh i soke vinograda, zelenoi masse pastbishchnykh trav, semenakh i masle rapsa, soi metodom kapilliarnoi gazozhidkostnoi khromatografii. Metodicheskie ukazaniia : utv. Rospotrebnadzorom 15.02.2007 [Determination of tau-fluvalinate residual amounts in grain and straw of cereals, in berries and grape juice, green mass of pasture grasses, seeds and oil of rapeseed, soybean by capillary gas-liquid chromatography. Methodical instructions: approved by Rospotrebnadzor 15.02.2007], “Russ. State Agrarian University - MAAA named after K.A. Timiryazev. Educational and scientific consulting center “Agroecology of pesticides and agrochemicals”, Moscow, RU, 2007.
10. Walorczyk S., “Development of a multi-residue screening method for the determination of pesticides in cereals and dry animal feed using gas chromatography–triple quadrupole tandem mass spectrometry”, Journal of Chromatography A, 2007, vol. 1165, no. 1–2, pp. 200–212.
11. Walorczyk S., “Development of a multi-residue method for the determination of pesticides in cereals and dry animal feed using gas chromatography–tandem quadrupole mass spectrometry. II. Improvement and extension to new analytes”, Journal of Chromatography A, 2008, vol. 1208, pp. 202–214.
12. Walorczyk S., Drożdżyński D., “Improvement and extension to new analytes of a multi-residue method for the determination of pesticides in cereals and dry animal feed using gas chromatography–tandem quadrupole mass spectrometry revisited”, Journal of Chromatography A, 2012, vol. 1251, pp. 219–231.
13. Qin Y., Zhao P., Fan S., Han Y., Li Y., Zou N., Song S., Zhang Y., Li F., Li X., Pan C., “The comparison of dispersive solid phase extraction and multi-plug filtration cleanup method based on multi-walled carbon nanotubes for pesticides multi-residue analysis by liquid chromatography tandem mass spectrometry”, Journal of Chromatography A, 2015, vol. 1385, pp. 1–11.
14. Kolberg D. I., Prestes O. D., Adaime M. B., Zanella R., “Development of a fast multiresidue method for the determination of pesticides in dry samples (wheat grains, flour and bran) using QuEChERS based method and GC–MS”, Food Chemistry, 2011, vol. 125, pp. 1436–1442.
15. Khan I. A. T., Parveen Z., Ahmed R., Ahmed M., “Multi-residue Determination of Organophosphorus Pesticides and Synthetic Pyrethroids in Wheat”, International Journal Of Agriculture And Biology, 2007, vol. 9, pp. 905–908.
16. Uddin R., Iqbal S., Baloch P. A., Bhutto A., Ahmed A., “Gas Chromatographic Multi-Residue Pesticide Determination Method for Cereal Grains”, American-Eurasian journal of agricultural & environmental sciences, 2015, vol. 15, pp. 1617–1624.
17. Wilkowska A., Biziuk M., “Determination of pesticide residues in food matrices using the QuEChERS methodology”, Food Chemistry, 2011, vol. 125, pp. 803–812.
18. Díez C., Traag W. A., Zommer P., Marinero P., Atienza J., “Comparison of an acetonitrile extraction/partitioning and “dispersive solid-phase extraction” method with classical multi-residue methods for the extraction of herbicide residues in barley samples”, Journal of Chromatography A, 2006, vol. 1131, pp. 11–23.
19. Zayats M. F., Leschev S. M., Zayats M. A., “A novel method of determination of some pesticides in vegetable oils based on dissociation extraction followed by gas chromatography/mass spectrometry”, Food Additives & Contaminants: Part A, vol. 33, no. 8, DOI: 10.1080/19440049.2016.1209575. Vol. 33. – P. 1337–1345.
20. “Guidance document on analytical quality control and method validation procedures for pesticides residues analysis in food and feed”, available at: http://ec.europa.eu/food/plant/docs/plant_pesticides_mrl_guidelines_wrkdoc_11945_en.pdf, (Accessed 19.04.2016).