Development of Multi-residue Analysis of 320 Pesticides in Apple and Rice Using LC-MS/MS and GC-MS/MS

LC-MS/MS와 GC-MS/MS를 이용한 사과와 쌀 시료에서 320종 농약의 다성분 분석

  • Kim, Jong-Hwan (Environmental Toxicology Research Center, Korea Institute of Toxicology) ;
  • Kim, Yeong-Jin (Environmental Toxicology Research Center, Korea Institute of Toxicology) ;
  • Kwon, Young-Sang (Environmental Toxicology Research Center, Korea Institute of Toxicology) ;
  • Seo, Jong-Su (Environmental Toxicology Research Center, Korea Institute of Toxicology)
  • 김종환 (안전성평가연구소 환경독성연구센터) ;
  • 김영진 (안전성평가연구소 환경독성연구센터) ;
  • 권영상 (안전성평가연구소 환경독성연구센터) ;
  • 서종수 (안전성평가연구소 환경독성연구센터)
  • Received : 2016.03.25
  • Accepted : 2016.06.17
  • Published : 2016.06.30


A new analytical method has been developed to determine 320 pesticides in apple and rice. The extraction of pesticides was carried out based on QuEChERS sample extraction, and determination was performed using LC-MS/MS and GC-MS/MS. 320 pesticides were selected for experiments. 251 and 110 pesticides among them were analysed by LC-MS/MS and GC-MS/MS, respectively. 41 pesticides of them were analyzed by both GC-MS/MS and LC-MS/MS. Among pesticides analysed by LC, 242 pesticides (96% of total number) in apple and 237 pesticides (94% of total number) in rice showed recoveries in the range of 70~120% with RSD ${\leq}20%$. In case of pesticides analyzed by GC-MS/MS, 103 pesticides (94% of total number) in apple and 83 pesticides (76% of total number) in rice were successfully validated. These results indicated that LC-MS/MS and GC-MS/MS analysis with the QuEChERS sample preparation can be partly applied to multi-residue pesticides in agricultural products.

본 연구는 사과와 쌀에서 320성분 농약에 대한 다성분 동시분석법을 확립하고자 수행되었다. 시료의 추출은 QuEChERS법을 사용하였고, 추출 후 잔류물은 LC-MS/MS와 GC-MS/MS로 기기분석 하였다. 시험 농약은 LC-MS/MS 251성분, GC-MS/MS 110성분을 선발하였으며, 41성분은 공통적으로 적용되었다. 분석법의 정량한계는 LC-MS/MS에서 $0.01{\sim}20{\mu}g/kg$, GC-MS/MS에서 $0.1{\sim}100{\mu}g/kg$으로 산출되었다. 사과와 쌀에서 회수율 70~120%, 상대표준편차 20% 이내의 조건을 충족한 성분은 LC-MS/MS로 분석한 농약 중 각각 242성분(96%)과 237성분(94%)로 나타났으며, GC-MS/MS로 분석한 농약 중에는 각각 103성분(94%)과 83성분(76%)로 나타났다. 본 연구를 통해 QuEChERS 전처리와 LC-MS/MS 및 GC-MS/MS를 이용한 분석법은 농산물(사과 및 쌀) 중 잔류농약 다성분 동시 분석에 효과적으로 적용될 것으로 기대된다.



Supported by : 안전성평가연구소


  1. Anastassiades, M., S. J. Lehotay, D. tajnbaher and F. J. Schenck (2003) Fast and Easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solidphase extraction” for the determination of pesticide residues in produce. Journal of AOAC International. 86:412-431.
  2. Bhanti, M. and A. Taneja (2007) Contamination of vegetables of different seasons with organophosphorous pesticides and related health risk assessment in northern India. Chemosphere 69(1):63-68.
  3. Cajka, T., J. Hajslova, O. Lacina, K. Mastovska and S. J. Lehotay (2008) Rapid analysis of multiple pesticide residues in fruit-based baby food using programmed temperature vaporiser injectionlow-pressure gas chromatography high-resolution time-of-flight mass spectrometry. Journal of Chromatography A 1186(1):281-294.
  4. Chamkasem, N., L. W. Ollis, T. Harmon, S. Lee and G. Mercer (2013) Analysis of 136 pesticides in avocado using a modified QuEChERS method with LC-MS/MS and GCMS/MS. Journal of agricultural and food chemistry 61(10):2315-2329.
  5. Cho, T. H., Y. H. Park, H. W. Park, L. H. Hwang, I. S. Cho, M. J. Kim, and Y. Z. Chae (2013) Evaluation of QuEChERS method for determination of pesticide residues using GC/NPD and GC/ECD. The Korean Journal of Pesticide Science 17(1):65-71.
  6. Codex Alimentarius Commission (2003) Guidelines on good laboratory practice in residue analysis. pp.25 CAC/GL 40-1993, Rev.1.
  7. Do, J. A., H. J. Lee, Y. W. Shin, W. J. Choe, K. R. Chae, C. S. Kang and W. S. Kim (2010) Monitoring of pesticide residues in domestic agricultural products. Journal of the Korean Society of Food Science and Nutrition 39(6):902-908.
  8. Fenik, J., M. Tankiewicz and M. Biziuk (2011) Properties and determination of pesticides in fruits and vegetables. Trac-Trends Anal. Chem. 30(6):814-826.
  9. Guana, H., W. E. Brewera, S. T. Garrisb and S. L. Morgana (2010) Disposable pipette extraction for the analysis of pesticides in fruit and vegetables using gas chromatography/mass spectrometry, Journal of Chromatography A 1217(12):1867-1874.
  10. Gwon, J. H., T. K. Kim, E. K. Seo, S. M. Hong, H. Y. Kwon, K. S. Kyung, J. E. Kim and N. J. Cho (2014). Multiresidue Analysis of 124 Pesticides in Soils with QuEChERS extraction and LC-MS/MS. Korean Journal of Pesticide Science 18(4):296-313.
  11. Hernando, M. D., J. M. Suarez-Barcena, M. J. M. Bueno, J. F. Garcia-Reyes and A. R. Fernandez-Alba (2007) Fast separation liquid chromatographytandem mass spectrometry for the confirmation and quantitative analysis of avermectin residues in food. Journal of Chromatography A 1155(1): 62-73.
  12. Ju, O. J., H. Y. Kwon, B. J. Park, C. S. Kim, Y. D. Jin, J. B. Lee and G. J. Im (2011) Analysis of 236 Pesticides in Apple for Validation of Multiresidue Method using QuEChERS Sample Preparation and PTV-GC/TOFMS Analysis. The Korean Journal of Pesticide Science 15(4):401-416.
  13. Koesukwiwat, U., S. J. Lehotay, K. Mastovska, K. J. Dorweiler and N. Leepipatpiboon (2010) Extension of the QuEChERS Method for Pesticide Residues in Cereals to Flaxseeds, Peanuts, and Doughs. Journal of Agricultural and Food Chemistry. 58:5950-5958.
  14. Kwon, H. Y., C. S. Kim, B. J. Park, Y. D. Jin, K. Son, S. M. Hong and G. J. Im (2011) Multiresidue analysis of 240 pesticides in apple and lettuce by QuEChERS sample preparation and HPLC-MS/MS analysis. The Korean Journal of Pesticide Science 15(4):417-433.
  15. Lee, E. Y., H. H. Noh, Y. S. Park, K. W. Kang, S. Y. Jo, S. R. Lee, I. Y. Park, T. H. Kim, Y. D. Jin and K. S. Kyung (2008) Monitoring of pesticide residues in agricultural products collected from markets in Cheongju and Jeonju. Kor. J. Pest. Sci. 12(4):357-362.
  16. Lee, Y. D (2012) Handbook for the pesticide residue analytical methods of Food Code Index. National Institution of Food and Drug Safety Evaluation
  17. Lee, D. Y., Y. J. Kim, M. H. Park, S. H. Lee, S. G. Kim, N. J. Kang and K. Y. Kang (2013) Establishment of Pre-Harvest Residue Limit (PHRL) of Fungicides Azoxystrobin and Difenoconazole on Prunus mume fruits. Kor. J. Pest. Sci. 17(4):307-313.
  18. Lehotay, S. J. (2003) Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaborative study, Journal of AOAC International 90(2):485-520.
  19. Lehotay, S. J., A. D. Kok, M. Hiemstra and P. V. Bodegraven (2005) 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. Journal of AOAC International 88(2):595-614.
  20. Lehotay, S. J., K. A. Son, H. Y. Kwon, U. Koesukwiwat, W. Fu, K. Mastovska, E. Hoh and N. Leepipatpiboon (2010) Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. Journal of Chromatography A. 1217:2548-2560.
  21. Pang G. F., C. L. Fan, Y. M. Liu, Y. Z. Cao, J. J. Zhang, B. L. Fu, X. M. Li, Z. Y. Li and Y. P. Wu (2006) Multi-residue method for the determination of 450 pesticide residues in honey, fruit juice and wine by double-cartridge solid-phase extraction/gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry Food Additives and Contaminants 23(8):777-810.
  22. Rural Development Administration (2009) Bulletin of Pesticide Registration Investigator (Guidance of pesticide residue test), Notice of Rural Development Administration No. 2009-1. Suwon, Korea.
  23. Sannino, A., L. Bolzoni and M. Bandini (2004) Application of liquid chromatography with electrospray tandem mass spectrometry to the determination of a new generation of pesticides in processed fruits and vegetables. Journal of Chromatography A 1036(2):161-169.
  24. Seo, E. K., T. K. Kim, S. M. Hong, H. Y. Kwon, J. H. Kwon, K. Son and D. H. Kim (2013) Analysis of Systemic Pesticide Imidacloprid and Its Metabolites in Pepper using QuEChERS and LC-MS/MS. The Korean Journal of Pesticide Science. 17(4):264-270.
  25. Yang, I. C., S. M. Hong, H. Y. Kwon, T. K. Kim and D. H. Kim (2013) Multi-residue Pesticide Analysis in Cereal using Modified QuEChERS Samloe Preparation Method. The Korean Journal of Pesticide Science 17(4):314-334.
  26. Zhang, K., J. W. Wong, P. Yang, K. Tech, L. A. DiBenedetto, N. S. Lee, D. G. Hayward, C. M. Makovi, A. J. Krynitsky, K. Banerjee, L. Jao, S. Dasgupta, M. S. Smoker, R. Simonds and A. Schreiber (2011) Multiresidue Pesticide Analysis of Agricultural Commodities Using Acetonitrile Salt-Out Extraction, Dispersive Solid-Phase Sample Clean-Up, and High-Performance Liquid Chromatography-Tandem Mass Spectrometry, Journal of Agricultural and Food Chemistry 59(14):7636-7646.

Cited by

  1. seed and its application for a natural detergent pp.00225142, 2017,
  2. Monitoring of Pesticide Residues in Immature Citrus Fruits and the Characteristics by Processing Methods vol.22, pp.4, 2018,
  3. 수출딸기 중 Cyenopyrafen과 Cyflumetofen의 잔류소실 특성평가 및 잔류농약 모니터링 vol.36, pp.4, 2016,
  4. 관주처리에 따른 양액재배 딸기의 농약잔류 특성 vol.62, pp.1, 2016,
  5. 농산물 및 경작지 토양 시료 중 Benzo(a)pyrene 신속잔류분석법 개선 연구 vol.39, pp.1, 2016,
  6. Determination of 113 pesticides in hot pepper powder in Korea vol.46, pp.2, 2021,
  7. Molecular mechanisms of developmental toxicities of azoxystrobin and pyraclostrobin toward zebrafish (Danio rerio) embryos: Visualization of abnormal development using two transgenic lines vol.270, pp.None, 2016,
  8. Monitoring of Pesticide Residues in Commonly Consumed Medicinal Agricultural Products Distributed in Seoul vol.25, pp.1, 2016,
  9. Simultaneous determination and dietary risk assessment of clethodim and its metabolites in different fruits and vegetables vol.38, pp.5, 2016,