The Korean Journal of Pesticide Science (농약과학회지)

The Korean Society of Pesticide Science (한국농약과학회)
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Multiresidue Analysis of 240 Pesticides in Apple and Lettuce by QuEChERS Sample Preparation and HPLC-MS/MS Analysis

QuEChERS 전처리법과 HPLC-MS/MS 기기분석을 이용한 사과와 상추 중 240종 농약의 동시분석

  • Kwon, Hye-Young (Department of Agro-food Safety, National Academy of Agriculture Science, Rural Development Administration) ;
  • Kim, Chan-Sub (Department of Agro-food Safety, National Academy of Agriculture Science, Rural Development Administration) ;
  • Park, Byung-Jun (Department of Agro-food Safety, National Academy of Agriculture Science, Rural Development Administration) ;
  • Jin, Yong-Duk (Department of Agro-food Safety, National Academy of Agriculture Science, Rural Development Administration) ;
  • Son, Kyung-Ae (Department of Agro-food Safety, National Academy of Agriculture Science, Rural Development Administration) ;
  • Hong, Su-Myeong (Department of Agro-food Safety, National Academy of Agriculture Science, Rural Development Administration) ;
  • Lee, Je-Bong (Department of Agro-food Safety, National Academy of Agriculture Science, Rural Development Administration) ;
  • Im, Geon-Jae (Department of Agro-food Safety, National Academy of Agriculture Science, Rural Development Administration)
  • 권혜영 (농촌진흥청 국립농업과학원 농산물안전성부) ;
  • 김찬섭 (농촌진흥청 국립농업과학원 농산물안전성부) ;
  • 박병준 (농촌진흥청 국립농업과학원 농산물안전성부) ;
  • 진용덕 (농촌진흥청 국립농업과학원 농산물안전성부) ;
  • 손경애 (농촌진흥청 국립농업과학원 농산물안전성부) ;
  • 홍수명 (농촌진흥청 국립농업과학원 농산물안전성부) ;
  • 이제봉 (농촌진흥청 국립농업과학원 농산물안전성부) ;
  • 임건재 (농촌진흥청 국립농업과학원 농산물안전성부)
  • Received : 2011.09.19
  • Accepted : 2011.11.06
  • Published : 2011.12.31
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Abstract

The study tested QuEChERS (quick, easy, cheap, effective, rugged and safe) sample preparation and HPLC-MS/ MS analysis for measurement of pesticide residues in fruit and vegetable. 240 kinds of pesticides spiked at three levels of 90, 45, 9 ng/g in lettuce and apple. For QuEChERS sample preparation, graphitized carbon black (GCB) was used for only lettuce in dispersive-SPE as absorbent. Matrix-matched standard calibration was used for quantitative analysis of HPLC-MS/MS. 218 pesticides (91%) in apple and 207 pesticides (86%) in lettuce showed recoveries in the range of 70~120% with $RSD{\leq}20%$. The lowest calibrated level (LCL) were 4.5 ng/g for 192 pesticides, 9 ng/g for 42 pesticides, 45 ng/g for 3 pesticides and 3 pesticides were not detected at all concentration levels. The results showed that the QuEChERS sample preparation and HPLC-MS/MS analysis can be applied to multi-residue analysis of pesticides in vegetables and fruits.

QuEChERS(quick, easy, cheap, effective, rugged and safe) 전처리법과 HPLC-MS/MS의 기기분석조건을 확립하고 분석법을 검증하였다. 상추와 사과에 첨가농도 90, 45, 9 ng/g로 농약을 처리하고 상추의 경우 GCB를 첨가하고 사과의 경우 GCB를 첨가하지 않고 QuEChERS법으로 전처리 한 후 HPLC-MS/MS로 분석하여 matrix matched calibration을 이용하여 회수율을 조사한 결과, 첨가된 농약 240성분 중 회수율이 70~120%이고 RSD가 20% 이하인 농약은 사과의 경우 218성분(91%), 상추의 경우 207성분(86%)이었다. 또한 lowest calibrated level(LCL)은 192성분이 4.5 ng/g, 42성분이 9 ng/g, 3성분이 45 ng/g이었으며 3성분은 검출이 불가능하였다. 따라서 본 시험에서 사용된 QuEChERS 전치리법과 HPLCMS/MS 분석조건을 이용하여 국내 등록 농약에 대한 야채와 과일중의 잔류농약 분석이 가능할 것으로 판단되었다.

Keywords

References

  1. Alder, L., K. Greulich, G. Kempe, B. Vieth (2006) Residue analysis of 500 high priority pesticides: Better by GC-MS or LC-MS/MS? Mass Sectrometry Reviews 25(2):838-865.
  2. Anastassiades, M., S. J. Lehotay, D. Stajnbaher, F. J. Schenck (2003) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and "dispersive solid-phase extraction" for the determination of pesticide residues in produce, J AOAC Int. 86(2):412-431.
  3. Anastassiades M, E. Scherbaum, D. Bertsh (2003) Validation of a simple and rapid multiresidue method and its implementation in routine pesticide analysis. MGPR Symposium, France.
  4. Anastassiades M, E. Scherbaum, D. Mack (2004) Implementation of the QuEChERS method for the routine analysis of pesticide residues-experiences and validation data, European Pesticide Residues Workshop, EPRW, Stockholm.
  5. Anastassiades, M. (2007) CEN Standard Method EN 15662: Food of plant origin-determination of pesticide residues using GC-MS and/or LC-MS (/MS) following acetonitrile extraction/partitioning and cleanup by dispersive SPE-QuEChERS method (http://www.cen.eu).
  6. Fillon J., F. Sauve, J. Selwyn (2000) Multiresidue method for the determination of residues of 251 pesticides in fruits and vegetables by gas-chromatography/mass spectromethry and liquid chromatography with fluorescence detection. Journal of AOAC International 83(3):698-713.
  7. Guana, H., W. E. Brewera, S. T. Garrisb, 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. https://doi.org/10.1016/j.chroma.2010.01.047
  8. Guana, H., W. E. Brewera, S. L. Morgana (2009) New Approach to Multiresidue Pesticide Determination in Foods with High Fat Content Using Disposable Pipette Extraction (DPX) and Gas Chromatography-Mass spectrometry (GC-MS), Journal of Agricultural and Food Chemistry 57(22):10531-10538. https://doi.org/10.1021/jf902373u
  9. Hernandoa, M. D., J. M. Suarez-Barcenab, M. J. M. Buenoa, J. F. Garcia-Reyesa, A. R. Fernandez-Alba (2007) Fast separation liquid chromatography-tandem mass spectrometry for the confirmation and quantitative analysis of avermectin residues in food, Journal of Chromatography A 1155(1):62-73. https://doi.org/10.1016/j.chroma.2007.02.120
  10. http://www.quechers.com
  11. http://www.mhlw.go.jp/topics/bukyoku/iyaku/syoku-anzen/zanryu3/siken.html#2
  12. Koesukwiwat, U., S. J. Lehotay , K. Mastovska, K. Dorweiler, N. Leepipatpiboon (2010) Extension of the QuEChERS Method for Pesticide Residues in Cereals to Flaxseeds, Peanuts, and Doughs. Journal of Agricultural and Food Chemistry 2010, 58:5950-5958. https://doi.org/10.1021/jf902988b
  13. Koesukwiwat, U., S. J. Lehotay, S. Miao, N. Leepipatpiboon (2010) High throughput analysis of 150 pesticides in fruits and vegetables using QuEChERS and low-pressure gas chromatography-time-of-flight mass spectrometry, Journal of Chromatography A 1217:6692-6703. https://doi.org/10.1016/j.chroma.2010.05.012
  14. Lee, S. M., M. L. Papathakis, H. C. Feng, G. F. Hunter, J. E. Carr (1991) Multipesticide residue method for fruits and vegetables: California Department of Food and Agriculture, Fresenius Journal of Analytical Chemistry 339:376-383. https://doi.org/10.1007/BF00322352
  15. Lee, S. W., J. H. Choi, S. K. Cho, H. Yu, A. M. Abd El-Aty, J. H. Shim (2011) Development of a new QuEChERS method based on dry ice for the determination of 168pesticides in Paprika using tandem mass spectrometry Journal of Chromatography A 1218; 4366-4377. https://doi.org/10.1016/j.chroma.2011.05.021
  16. Lehotay, S. J. (2007) Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaborative study. Journal of AOAC International 90(2):485-520.
  17. Lehotay, S. J., K. A. Son, H. Kwon, U. Koesukwiwat, W. Fu, K. Mastovska, E. Hoh, 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. https://doi.org/10.1016/j.chroma.2010.01.044
  18. Lehotay, S.J., A. De Kok, M. Hiemstra, P. V. Bodegraven (2005) Validation of a fast and easy method for the determination of 229 pesticide residues in fruits and vegetables using gas and liquid chromatography and mass spectrometric detection. Journal of Association of Official Analytical Chemists International 88:595-614.
  19. Luke, M. A., J. E. Froberg, H. T. Masumoto (1975) Extraction and cleanup of organochlorine, organophosphate, organonitrogen, and hydrocarbon pesticides in produce for determination by gas-liquid chromatography, Journal of the Association of Official Analytical Chemists 58(5):1020-1026.
  20. Luck, M. A., J.E. Froberg, G. M. Doose, H.T. Masumato (1981) Improved multiresidues gas chromatographic determination of organo phosphorous, organonitrogen and organohalogen pesticides in products using flame photometric and electrolytic conductivity detectors. Journal of the Association of Official Analytical chemists 64:1187-1195.
  21. Mastovska, K., S. J. Lehotay (2004) Evaluation of common organic solvent for gas chromatographic analysis and stability of multiclass pesticides, Journal of Chromatography A 1040; 259-272. https://doi.org/10.1016/j.chroma.2004.04.017
  22. Mills, P. A., J. J. Onley, R. A. Gaither (1963) Rapid method for chlorinated pesticide residues in non-fatty foods, Journal of the Association of Official Analytical Chemists 46(2):186-191.
  23. Schenck, F. J., J. E. Hobbs (2008) Evaluation of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) Approach to Pesticide Residue Analysis, Bulletine of Environmental Contaminaton and Toxicology 73:24-30.
  24. Walorczyk, S. (2008) Application of gas chromatography/tandem quadrupole mass spectrometry to the multi-residue analysis of pesticides in green leafy vegetables, Rapid communication in mass spectrometry, 22:3791-3801. https://doi.org/10.1002/rcm.3800
  25. 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, 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. https://doi.org/10.1021/jf2010723
  26. 농촌진흥청, 2010, 농약관리법령 및 고시.훈령집.
  27. 식품의약품안전청, 2011, 식품공전, 제 10. 일반시험법, 4. 식품 중 잔류농약 분석법.
  28. 식품의약품안전평가원, 2009, 식품공전 잔류농약 분석법 실무해설서.
  29. 주옥정, 권혜영, 박병준, 김찬섭, 진용덕, 이제봉, 윤서희, 손경애, 홍수명, 임건재 (2011) QuEChERS법과 PTV-GC/TOFMS이용 잔류농약 분석법 개발을 위한 사과시료 중 236종 농약의 동시 분석, 한국농약과학회지 15(4) 401-416.