Journal of the Korean Society of International Agriculture (한국국제농업개발학회지)

The Korean Society of International Agriculture (한국국제농업개발학회)
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Development of Individual Residue Analysis Method for Cyanazine in Agricultural Commodities as an Unregistered Herbicide in Korea

국내 미등록 제초제 cyanazine의 농산물 중 개별 잔류분석법 개발

  • 정명근 (강원대학교 생약자원개발학과) ;
  • 임무혁 (대구대학교 식품공학과)
  • Received : 2018.11.13
  • Accepted : 2018.12.13
  • Published : 2018.12.31
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Abstract

Cyanazine is a member of the triazine family of herbicides. Cyanazine is used as a pre- and post-emergence herbicide for the control of annual grasses and broadleaf weeds. This experiment was conducted to establish a determination method for cyanazine, as domestic unregistered pesticide, residue in major agricultural commodities using HPLC-DAD/MS. Cyanazine was extracted with acetone from representative samples of five raw products which comprised apple, green pepper, Kimchi cabbage, hulled rice and soybean. The extract was diluted with saline water and partitioned to dichloromethane for remove polar extractive in the aqueous phase. For the hulled rice and soybean samples, n-hexane/acetonitrile partition was additionally employed to remove non-polar lipids. The extract was finally purified by optimized florisil column chromatography. On a $C_{18}$ column in HPLC, cyanazine was successfully separated from co-extractives of sample, and sensitively quantitated by diode array detection at 220 nm. Accuracy and precision of the proposed method was validated by the recovery experiment on every major agricultural commodity samples fortified with cyanazine at 3 concentration levels per agricultural commodity in each triplication. Mean recoveries were ranged from 83.6 to 93.3% in five major representative agricultural commodities. The coefficients of variation were all less than 10%, irrespective of sample types and fortification levels. Limit of quantitation(LOQ) of cyanazine was 0.02 mg/kg as verified by the recovery experiment. A confirmatory method using LC/MS with selected-ion monitoring(SIM) technique was also provided to clearly identify the suspected residue.

본 연구는 HPLC-DAD/MS를 이용하여 농산물 중 triazine계 제초제인 cyanazine의 잔류 분석법을 확립하였다. 대표 농산물은 사과, 배추, 고추, 현미 및 콩을 선정하였고, 아세톤을 첨가하여 추출된 cyanazine 성분을 dichloromethane 액-액 분배법과 florisil 흡착크로마토그래피법으로 정제하여 HPLC-DAD/MS 분석대상의 시료로 사용하였다. Cyanazine의 정량적 분석을 위한 최적 HPLC-DAD/MS 분석조건을 확립하였으며, 정량한계(LOQ)는 0.02 mg/kg 이었다. 각 대표 농산물에 대해 정량한계, 정량한계의 10배 및 50배 수준에서 회수율을 검토한 결과, 모든 처리농도에서 83.6~93.3% 수준을 나타내었으며, 반복 간 변이계수(CV)는 최대 2.8%를 나타내어 잔류분석 기준인 회수율 70~120% 및 분석오차 10% 이내를 충족시키는 만족한 결과를 도출하였고, 또한 LC/MS SIM을 이용하여 실제 농산물 시료에 적용하여 재확인 하였다. 이상의 결과로 신규 cyanazine의 HPLC-DAD/MS 분석법은 검출한계, 회수율 및 분석오차 면에서 국제적 분석기준을 만족하는 신뢰성이 확보된 정량 분석법으로 사용 가능할 것이다.

Keywords

References

  1. AOAC. 2000. Pesticide and industrial chemical residues, In Official method of analysis, pp. 1-88. 17th ed., AOAC International, Arlington, VA, USA.
  2. Codex Alimentarius Commission. 2003. Guidelines on Good Laboratory Practice in Residue Analysis, CAC/GL 40-1993, Rev.1-2003, Rome, Italy.
  3. Hogendoorn, E.A., & Goewie, C.E. 1989. Residue analysis of the herbicides cyanazine and bentazone in sugar maize and surface water using high-performance liquid chromatography and an online clean-up column-switching procedure. Journal of Chromatography 475: 432-441. https://doi.org/10.1016/S0021-9673(01)89700-4
  4. Hwang, Y.S., Lim, J.D., & Choung, M.G. 2016. Analytical method for triazine herbicide cyanazine residues in major medicinal crops. Korean Journal of Medicinal Crop Science 14(3): 237-245.
  5. 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 & Technology 21(6): 518-525.
  6. Lee, J.H., Park, H.W., Keum, Y.S., Kwon, C.H., Lee, Y.D., & Kim, J.H. 2008. Dissipation pattern of boscalid in cucumber under greenhouse condition. Korean Journal of Pesticide Science 12(1): 67-73.
  7. Lee, S.J., Hwang, Y.S., Kim, Y.H., Nam, M.Y., Hong, S.B., Yun, W.K., Kwon, C.H., Do, J.A., Im, M.H., Lee, Y.D., & Choung, M.G. 2010. Determination of formesafen residue in agricultural commodities using HPLC-UVD/MS, Korean Journal of Pesticide Science 14(2): 100-108.
  8. Lee, S.J., Kim, Y.H., Song, L.S., & Choung, M.G. 2011 a. Determination of ametryn residue in agricultural commodities using HPLC-UVD/MS, Korean Journal of Pesticide Science 15(2): 125-133.
  9. Lee, S.J., Kim, Y.H., Song, L.S., Hwang, Y.S., Lim, J.D., Sohn, E.H., Im, M.H., Do, J.A., Oh, J.H., Kwon, K.S., Lee, J.K., Lee, Y.D., & Choung, M.G. 2011 b. Development of analytical method for fenoxycarb, pyriproxyfen and methoprene residues in agricultural commodities using HPLC-UVD/MS. Korean Journal of Pesticide Science 15(3): 254-268.
  10. Lee, Y.D. 2017. Pesticide Analytical Residues Manual in Food Code. Ministry of Food and Drug Safety, Seoul, Korea.
  11. Lynch, S.M., Rusiecki, J.A., Blair, A., Dosemeci, M., Lubin, J., Sandler, D., Hoppin, J.A., Lynch, C.F., & Alavanja, M.C. 2006. Cancer incidence among pesticide applicators exposed to cyanazine in the agricultural health study. Environmental Health Perspectives 114(8): 1248-1252. https://doi.org/10.1289/ehp.8997
  12. McLafferty, F.W., & Turecek, F. 1993. Interpretation of mass spectra, pp. 19-50, 4th ed. Sausalito, CA, USA.
  13. Meador, M., & Jie, M. 2014. Maximum residue limits for pesticides in food, p. 130, Beijing, China.
  14. NewZealand Food Safety Authority. 2007. Technical information sheets for purposed MRLs, p. 8.
  15. Ministry of Food and Drug Safety. 2017. Korea Food Code, pp. 10-4-340-10-4-342.
  16. Park, H.K., Noh, H.H., Lee, K.H., Lee, J.Y., Park, Y.S., Kang, K.W., Lee, E.Y., Yun, S.S., Jin, C.W., & Kyung, K.S. 2011. Residual characteristic of chlorpyrifos in squash and estimation of its residues before harvest, Korean Journal of Pesticide Science 15(4): 463-470.
  17. Sanchez-Rasero, F., & Dios, G.C. 1988. Liquid chromatographic method for the determination of cyanazine in the presence of some normal soil constituents, Journal of Chromatography 447: 426-431. https://doi.org/10.1016/S0021-9673(01)91506-7
  18. US FDA. 1999. Pesticide Analytical Manual, Vol 1: Multi-residue Methods (3rd ed.), US Food and Drug Administration, USA.
  19. World Health Organization. 2003. Cyanazine in drinking-water, Background document for development of WHO guidelines for drinking-water quality, p. 1, 2nd ed. Geneva, Switzerland.
  20. Zhang, G., & Pan, J. 2011. Simultaneous spectrophotometric determination of atrazine and cyanazine by chemometric methods, Spectrochimica Acta Part A. 78, 238-242. https://doi.org/10.1016/j.saa.2010.09.028