Development of a Residue Analysis Method for Metamifop in Paddy Water, Soil, and Rice with HPLC

HPLC를 이용한 농업용수, 논토양, 및 현미 중 metamifop의 잔류분석법 개발

  • Park, Hee-Woon (Korea Ginseng Corporation Research Institute, Korea Ginseng Corporation) ;
  • Moon, Joon-Kwan (Department of Plant Life and Environmental Sciences, Hankyong National University)
  • 박희원 ((주)한국인삼공사 R&D본부) ;
  • 문준관 (한경대학교 식물생명환경과학과)
  • Received : 2017.03.04
  • Accepted : 2017.03.20
  • Published : 2017.03.31


An analytical method for detecting metamifop residue in paddy water, soil, and rice with high performance liquid chromatography (HPLC) was developed. Water was extracted with ethyl acetate before analyzing by HPLC. Soil residues were extracted with acetone under acidic condition and after purifying with $Extrelut^{(R)}$ NT, and silica SPE, the residue was analyzed by HPLC. For residue analysis in rice, the procedure involved extraction with acetone, purification with $Extrelut^{(R)}$ NT, partitioning between acetonitrile/hexane, purification with silica SPE cartridge, and analysis by HPLC. The limit of detection (LOD) was 1.0 ng, limit of quantitation (LOQ) was 3.0 ng, and method limit of quantitation (MLOQ) were 0.001 mg/L for paddy water, 0.01 mg/kg for rice and soil, respectively. Standard calibration curve shows linearity from 0.05 mg/kg to 5.0 mg/kg ($R^2=0.9999$). The recoveries in fortified paddy water were $91.3{\pm}3.5%$ (0.01 mg/L level) and $93.2{\pm}6.3%$ (0.05 mg/L level). The recoveries in fortified paddy soils were $92.5{\pm}4.0%$ (0.1 mg/kg level) and $92.7{\pm}4.0%$ (0.5 mg/kg level) in soil A, while, $102.3{\pm}4.4%$ (0.1 mg/kg level) and $98.9{\pm}7.9%$ (0.5 mg/kg level) in soil B, respectively. The recoveries in fortified rice were $93.0{\pm}6.9%$ (0.1 mg/kg level) and $85.0{\pm}3.5%$ (0.5 mg/kg level). This method was proved to be effective and can be used to determine the metamifop residue in paddy water, paddy soil, and rice.




  1. Ahmed, F. E. (2003) Analysis of polychlorinated biphenyls in food products. Trends Anal. Chem. 22:170-185.
  2. Celi, L., M. Negre and M. Gennari (1993) HPLC determination of fenoxaprop and fenoxaprop-ethyl in different soils. Pest Manag. Sci. 38:43-47.
  3. Chang, H.S., K. H. Chung, Y. K. Ko, J. W. Ryu, J. C. Woo, D. W. Koo, Y. H. Kang, T. J. Kim, J. S. Kim, B. J. Chung, O. Y. Kwon and D. H. Kim (2004) Synthesis and herbicidal activities of 2-[4-(6-chloro-2-benzoxazolyloxy)phenoxy]-propionamide derivatives. Korean J Pestic. Sci. 8:145-149.
  4. Choi, J. S., C. M. Ryu, B.S. Han, D. H. Lee and I. T. Hwang (2011) Biochemical crop protecting agents for LOHAS, KIC News. 14:29-40.
  5. Garcia-Reyes, J. F., C. Ferrer, M. J. Gomez-Ramos, A. Molina-Diaz and A. R. Fernandez-Alba (2007) Determination of pesticide residues in olive oil and olives. Trends Anal. Chem. 26:239-251.
  6. Grimmer, G., G. Dettbarn and J. Jacob (1993) Biomonitoring of polycyclic aromatic hydrocarbons in highly exposed coke plant workers by measurement of urinary phenanthrene and pyrene metabolites (phenols and dihydrodiols). Int. Arch. Occup. Environ. Health. 65:189-199.
  7. Ito, S., K. Kudo, T. Imamura, T. Suzuki and N. Ikeda (1998) Sensitive determination of methomyl in blood using gas chromatography-mass spectrometry as its oxime tertbutyldimethylsilyl derivative. J. Chromatogr. B 713:323-330.
  8. KCPA (2016) Using guideline of crop protection agents. Korea Crop Protection Association, Samjung Inc. Seoul, Korea. p831.
  9. Kim, D. W., H. S. Chang, Y. K. Ko, J. W. Ryu, J. C. Woo, D. W. Koo and J. S. Kim (2003) Herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds. US Patent 6600048.
  10. Kudo, K., T. Ishida, N. Nishida, N. Yoshioka, H. Inoue, A. Tsuji and N. Ikeda N (2006) Simple and sensitive determination of free and total morphline in human liver and kidney using gas chromatography-mass spectrometry. J. Chromatogr. B 830:359-363.
  11. Lee, H., M. Riu, E. Kim, J. K. Moon, H. Choi, J. A. Do, J. H. Oh, K. S. Kwon, Y. D. Lee, and J. H. Kim (2013) A single residue method for the determination of chlorpropham in representative crops using high performance liquid chromatography, J. Korean Soc. App. Biol. Chem. 56:181-186.
  12. Leuenberger, U., R. Gauch and Baumgartner (1979) Determination of food presevatives and saccharin by highperformance liquid chromatography. J. Chromatogr. 173: 343-348.
  13. Moon, J. K., Y. S. Keum, E. C. Hwang, B. S. Park, H. R. Chang, Q. X. Li and J. H. Kim (2007) Hapten synthesis and antibody generation for a new herbicide, metamifop. J. Agric. Food Chem. 55:5419-5422.
  14. Moon, J. K., J. H. Kim and T. Shibamoto (2010) Photodegradation pathway and mechanism of the herbicide metamifop in water/acetonitrile solution. J. Agric. Food Chem. 58: 12357-12365.
  15. Muccio, A. D., A. M. Cicero, A. Ausili and S. D. Muccio(2005) Determination of organophosphorus pesticide residues in vegetable oils by single-step multicartridge extraction and cleanup and by gas chromatography with flame photometric detector. Pesticide proctocols. Vol. 19. In Methods in biotechnology; Martinez, J. L. and A. G. Frenich Eds; Humana Press Inc.; Totowa, NJ, U.S.A. pp. 263-271
  16. Park, H. W. (2004) Metabolism of a new herbicide metamifop in rats. Thesis of mater degree, Seoul National University.
  17. Pietta, P. G., P. L. Mauri and A. Rava (1990) Analysis of terpens from Ginkgo Biloba L. extracts by reversed phase highperormance liquid chromatography. Chromatographia 29: 251-253.
  18. Somers, D. A. (1996) Aryloxyphenoxypropionate and cyclohexanedione resitant crops. In Herbicide resistant crops. Duke, S. O. Eds; Lewis Publishers, Boca Raton, FL, U.S.A. p184.
  19. Tomlin, C. D. S. (2009) Metamifop, In A world compendium The Pesticide Manual 15th ED.; Tomlin, C.D.S. Eds; British Crop Protection Council, Alton, Hampshire, UK. p744.