Journal of Food Hygiene and Safety (한국식품위생안전성학회지)

The Korean Society of Food Hygiene and Safety (한국식품위생안전성학회)
권호 표지
DOI QR코드

DOI QR Code

Development of a Simultaneous Analytical Method for Determination of Herbicide Fenquinotrione and KIH-3653-M-2 Residues in Agricultural Crops using LC-MS/MS

LC-MS/MS를 이용한 농산물 중 제초제 fenquinotrione 및 대사산물 KIH-3653-M-2 동시시험법 개발

  • Park, Ji-Su (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, 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) ;
  • Lee, Han Sol (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Cho, Sung Min (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Shin, Hye-Sun (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Jang, Dong Eun (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, Kangbong (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety)
  • 박지수 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 도정아 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 이한솔 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 조성민 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 신혜선 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 장동은 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 정용현 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 이강봉 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과)
  • Received : 2019.03.04
  • Accepted : 2019.04.26
  • Published : 2019.06.30
Download PDF
⟨ Previous Next ⟩

Abstract

An analytical method was developed for the determination of fenquinotrione, a triketone herbicide, in agricultural products. Fenquinotrione was metabolized to KIH-3653-M-2 in plants. Analyte extraction was conducted using 2% formic acid in acetonitrile and cleaned up using a hydrophillic-lipophillic balance (HLB) cartridge. The limits of detection (LOD) and quantification (LOQ) were 0.004 and 0.01 mg/kg, respectively. Matrix-matched calibration curves were linear over the calibration ranges ($0.001{\sim}0.1{\mu}g/mL$) into a blank extract with $r^2>0.99$. The recovery results for fenquinotrione and KIH-3653-M-2 ranged between 81.1 to 116.2% and 78.0 to 110.0% at different concentration levels (LOQ, $10{\times}LOQ$, $50{\times}LOQ$) with relative standard deviation (RSD) less than 4.6%. All values were corresponded with the criteria ranges requested in both the Codex (CAC/GL 40-1993, 2003) and MFDS guidelines (2016). Therefore, the proposed method can be used as an official analytical method for determination of fenquinotrione in the Republic of Korea.

본 연구는 농산물 중 기준신설 예정농약 fenquinotrione에 대한 공정시험법을 개발하고자 수행하였다. Fenquinotrione은 triketone계 제초제로 quinoxaline 구조에 phenyl기가 치환된 새로운 구조의 화합물이며 대사산물 KIH-3653-M-2는 fenquinotrione의 quinoxaline 구조에 cyclohexadione이 -COOH로 치환되어 생성된다. 잔류물의 정의는 fenquinotrione 및 대사산물(KIH-3653-M-2)의 합으로 규정하여 관리할 예정이다. 본 연구에서는 향후 대사산물 안전관리를 고려하여 fenquinotrione 및 KIH-3653-M-2의 동시시험법을 확립하고자 하였다. 2% 포름산 함유한 아세토니트릴로 추출 후 무수황산마그네슘($MgSO_4$) 및 염화나트륨(NaCl) 첨가하여 간섭물질을 효과적으로 제거하고, HLB 카트리지를 이용하여 정제 후 LC-MS/MS로 분석하는 시험법을 개발하였다. 개발된 fenquinotrione 및 KIH-3653-M-2 동시시험법의 직선성은 결정계수($r^2$)가 0.99이상으로 우수하였으며, 검출한계 및 정량한계는 각각 0.004, 0.01 mg/kg이었다. 시험법 검증 결과 농산물 5품목에 대하여 평균 회수율(5반복)은 fenquinotrione 81.1~116.2%, KIH-3653-M-2의 평균 회수율은 78.0~110.0%이었다. RSD는 모두 4.6% 이하로 정확성, 정밀성 및 반복성이 우수함을 확인할 수 있었다. 본 연구 결과는 국제식품규격위원회 가이드라인(Codex Alimentarius Commission)의 잔류농약 분석 기준(CAC/GL 40-1993, 2003) 및 식품의약품안전평가원의 '식품등 시험법 마련 표준절차에 관한 가이드라인(2016)'에 부합하였다. 개발된 시험법은 낮은 검출한계 및 정량한계, 우수한 직선성, 회수율 실험을 통한 정확성과 정밀성, 재현성 등이 검증되어 농산물 중 fenquinorione의 잔류검사를 위한 공정시험법으로 활용가능 할 것이다.

Keywords

References

  1. Lee, I.Y., Kim, J.W., Kim, S.S., Yoo, J.H., Hwang, I.S., Lee, K.H., Cho, N.G., Lee, D.G., Hwang, K.H., Won, O.J., Weiqiang, J., Ko, Y.K., Choi, J.S., Yeom, H.S., Park, K.W.: Current Status and perspectives of Weed Science in Asia-Pacific Area. Weed and Turfgrass Science., 6(4), 292-305 (2017). https://doi.org/10.5660/WTS.2017.6.4.292
  2. Food Safety Commission of Japan(FSCJ): Risk assessment report-fenquinotrione. Food Safety, 5(3), 110-113 (2017) https://doi.org/10.14252/foodsafetyfscj.2017006s
  3. Ministry of Food and Drug Safety (MFDS), Korea food code. pp. 634-636 (2018)
  4. Ministry of Food and Drug Safety (MFDS), Korea food code. pp. 759-761 (2018)
  5. Luciana, G.F., Christian, W.G., Matthias, R., Heinz, P.S., Stephan, R.M.: Quantification of the new triketone herbicides, sulcotrione and mesotrione, and other important herbicides and metabolites, at the ng/L level in surface waters using liquid chromatography-tamdem mass spectrometry. J. Chromato. A., 1028, 277-286 (2004) https://doi.org/10.1016/j.chroma.2003.11.094
  6. Hanna, B., Marcin, S., Kornelia, S., Angelika, S., Martyna, T., Magdalena, K.: Atrazine, triketone herbicides, and their degradation products in sediment, soil and surface water samples in Poland. Environ. Sci. Pollut. Res., 24, 644-658 (2017) https://doi.org/10.1007/s11356-016-7798-3
  7. Guidelines on good laboratory practice in residue analysis, CAC/GL 40-1993. CAC (Codex Alimentarius Commission), Rome, Italy (2003).
  8. Guidelines on standard procedures for preparing analysis methods. Ministry of Food and Drug Safety (MFDS), Cheongju, Korea (2016).
  9. Ministry of Food and Drug Safety (MFDS), Pesticide analytical residues manual in food code. pp. 13-14 (2013).
  10. Kim, J.Y., Choi, Y.J., Kim, J.S., Kim, D.H., Do, J.A., Jung, Y.H., Lee, K.B., Kim, H.C.: Study for Residue Analysis of Herbicide, Clopyralid in Foods. Kor. J. Environ. Agric., 37(4), 283-290 (2018) https://doi.org/10.5338/KJEA.2018.37.4.42
  11. Ko, A.Y., Abd El-Aty, A.M., Rahman, M.M., Jang, J., Kim, S.W., Choi, J.H., Shim, J.H.: A modified QuEChERS method for simultaneous determination of flonicamid and its metabolites in paprika using tandem mass spectrometry. Food Chem., 157, 413-420 (2014). https://doi.org/10.1016/j.foodchem.2014.02.038
  12. Lehotay, S.J.: Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaboratice study. J. AOAC Intern., 90(2), 485-520 (2007) https://doi.org/10.1093/jaoac/90.2.485
  13. Anastassiades, M., Lehotay, S. J., Tajnbaher, D., Schenck, F.J.: Fast and Easy multiresidue method employing acetonitrile extraction/partitioning and "dispersive solid phase extraction" for the determination of pesticide residues in produce. J. AOAC Intern., 86, 412-431 (2003) https://doi.org/10.1093/jaoac/86.2.412