Korean Journal of Environmental Agriculture (한국환경농학회지)

The Korean Society of Environmental Agriculture (한국환경농학회)
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Study for Residue Analysis of Herbicide, Clopyralid in Foods

식품 중 제초제 클로피랄리드(Clopyralid)의 잔류 분석법

  • Kim, Ji-young (Division of Import Food Analysis, Ministry of Food and Drug Safety-Seoul Region, Ministry of Food and Drug Safety) ;
  • Choi, Yoon Ju (Food Standard Division, Food Standard Planning, Ministry of Food and Drug) ;
  • Kim, Jong Su (Division of Import Food Analysis, Ministry of Food and Drug Safety-Seoul Region, Ministry of Food and Drug Safety) ;
  • Kim, Do Hoon (Division of Import Food Analysis, Ministry of Food and Drug Safety-Seoul Region, Ministry of Food and Drug Safety) ;
  • Do, Jung Ah (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Jung, Yong Hyun (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Lee, Kang Bong (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Kim, Hyo Chin (Division of Import Food Analysis, Ministry of Food and Drug Safety-Seoul Region, Ministry of Food and Drug Safety)
  • 김지영 (식품의약품안전처 서울지방식품의약품안전청 수입식품분석과) ;
  • 최윤주 (식품의약품안전처 기준기획관실 식품기준과) ;
  • 김종수 (식품의약품안전처 서울지방식품의약품안전청 수입식품분석과) ;
  • 김도훈 (식품의약품안전처 서울지방식품의약품안전청 수입식품분석과) ;
  • 도정아 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 정용현 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 이강봉 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 김효진 (식품의약품안전처 서울지방식품의약품안전청 수입식품분석과)
  • Received : 2018.11.08
  • Accepted : 2018.12.10
  • Published : 2018.12.31
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Abstract

BACKGROUND: Pesticide residue analysis is an essential activity in order to establish the food safety of agricultural products. Analytical approaches to the food safety are required to meet internationally the guideline of Codex (Codex Alimentarius Commission, CAC/GL 40). In this study, we developed a liquid chromatograph-tandem mass spectrometer (LC-MS/MS) method to determine the herbicide clopyralid in food matrixes. METHODS AND RESULTS: Clopyralid was extracted with aqueous acetonitrile containing formic acid and the extracts were mixed in a citrate buffer consisted of magnesium sulfate anhydrous, NaCl, sodium citrate dihydrate and disodium hydrogencitrate sesquihydrate followed by centrifugation. The supernatants were filtered through a nylon membrane filter and used for the analysis of clopyralid. The method was validated by accuracy and precision experiments on the samples fortified at 3 different levels of clopyralid. LC-MS/MS in positive mode was employed to quantitatively determine clopyralid in the food samples. Matrix-matched calibration curves were inearranged from 0.001 to 0.25 mg/kg with r2 > 0.994. The limits of detection and quantification were determined to be 0.001 and 0.01 mg/kg, respectively. There covery values of clopyralid for tified at 0.01 mg/kg in the control samples ranged from approximately 82 to 106% with relative standard deviations below 2 0%. CONCLUSION: The method developed in this study meets successfully the Codex guideline for pesticide residue analysis in food samples. This, the method could be applicable to determine pesticides in foods produced domestically and internationally.

본 연구는 LC-MS/MS법을 적용하여 농산물에 함유된 pyridine계통의 제초제 Clopyralid의 잔류분석법을 확립하였다. 대표적인 농산물로는 귤, 고추, 대두, 감자 및 현미를 선정하였고 acetonitrile에 의해 추출된 성분을 QuEChERS법을 변경하여 정제법으로 사용하고 LC-MS/MS를 사용하여 분석법을 확립하였다. Clopyralid의 정량적 분석을 위한 최적 분석 조건을 확립하였으며, 검출한계는 0.001 mg/kg, 정량 한계(LOQ)는 0.01 mg/kg이었다. 각 대표 농산물에 대한 정량한계, 정량한계의 10배, 50배 수준에서 회수율을 검토한 결과 모든 처리 농도에서 81.7~105.8 %수준을 나타내었으며, 모든 수준에서 20 % 미만의 분석오차를 나타내어 잔류분석기준을 만족하였다. 본 연구에서 확립된 Clopyralid분석법은 검출한계, 회수율 및 분석오차에서 국제적 분석기준을 만족하는 분석법으로 농산물에 따라 정량분석법으로 사용 가능할 것으로 사료된다.

Keywords

References

  1. Ahn, K. G., Kim, G. H., Kim, G. P., Kim, M. J., Hwang, Y. S., Hong, S. B., Lee, Y. D., & Choung, M. G. (2014). Determination of amisulbrom residues in agricultural commodities using HPLC-UVD/MS. The Korean Journal of Pesticide Science, 18(4), 321-329. https://doi.org/10.7585/kjps.2014.18.4.321
  2. Cremlyn, R. J. (1991). Agrochemicals: Preparation and mode of action, pp. 219-227, John Wiley & Sons, Chichester, UK.
  3. Koesukwiwat, U., Sanguankaew, K., & Leepipatpiboon, N. (2008). Rapid determination of phenoxy acid residues in rice by modified QuEChERS extraction and liquid chromatography-tandem mass spectrometry. Analytica Chimica Acta, 626(1), 10-20. https://doi.org/10.1016/j.aca.2008.07.034
  4. Kwon, C. H., Chang, M. I., Im, M. H., Choi, H., Jung, D. I., Lee, S. C., Yu, J. Y., Lee, Y. D., Lee, J. O., & Hong, M. K. (2008). Determination of mandipropamid residues in agricultural commodities using high-performance liquid chromatography with mass spectrometry. Analytical Science and Technology, 21(6), 518-525.
  5. Lee, S. J., Hwang, Y. S., Kim, Y. H., Kwon, C. H., Do, J. A., Im, M. H., Lee, Y. D., & Choung, M. G. (2010). Determination of Captan, Folpet, Captafol and Chlorothalonil residues in agricultural commodities using GC-ECD/MS. Korean journal of environmental agriculture, 29(2), 165-175. https://doi.org/10.5338/KJEA.2010.29.2.165
  6. Lin, C. H., Lerch, R. N., Thurman, E. M., Garrett, H. E., & George, M. F. (2002). Determination of isoxaflutole (Balance) and its metabolites in water using solid phase extraction followed by high-performance liquid chromatography with ultraviolet or mass spectrometry. Journal of Agricultural and Food Chemistry, 50(21), 5816-5824. https://doi.org/10.1021/jf025622d
  7. Mastovska, K., Dorweiler, K. J., Lehotay, S. J., Wegscheid, J. S., & Szpylka, K. A. (2010). Pesticide multiresidue analysis in cereal grains using modified QuEChERS method combined with automated direct sample introduction GC-TOFMS and UPLC-MS/MS techniques. Journal of Agricultural and Food Chemistry, 58(10), 5959-5972. https://doi.org/10.1021/jf9029892
  8. Sack, C., Vonderbrink, J., Smoker, M., & Smith, R. E. (2015). Determination of acid herbicides using modified QuEChERS with fast switching ESI+/ESI-LC-MS/MS. Journal of Agricultural and Food Chemistry, 63(43), 9657-9665. https://doi.org/10.1021/acs.jafc.5b04093
  9. Schutz, S., Vedder, H., During, R. A., Weissbecker, B., & Hummel, H. E. (1996). Analysis of the herbicide clopyralid in cultivated soils. Journal of Chromatography A, 754(1-2), 265-271. https://doi.org/10.1016/S0021-9673(96)00156-2