Journal of Food Hygiene and Safety (한국식품위생안전성학회지)

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

DOI QR Code

Selection and Validation of an Analytical Method for Trifludimoxazin in Agricultural Products with LC-MS/MS

LC-MS/MS를 이용한 농산물 중 Trifludimoxazin의 시험법 선정 및 검증

  • Sun Young Gu (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Su Jung Lee (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • So eun Lee (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Chae Young Park (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 Mi Lee (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Inju Park (Imported Food Analysis Division, Seoul Regional Food and Drug Administration) ;
  • Yun Mi Chung (Hazardous Substances Analysis Division, Gwangju Regional Food and Drug Administration) ;
  • Gui Hyun Jang (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Guiim Moon (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety)
  • 구선영 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 이수정 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 이소은 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 박채영 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 이정미 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 박인주 (식품의약품안전처 서울지방식품의약품안전청 식품기준분석과) ;
  • 정윤미 (식품의약품안전처 광주지방식품의약품안전청 유해물질분석과) ;
  • 장귀현 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 문귀임 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과)
  • Received : 2023.01.10
  • Accepted : 2023.06.02
  • Published : 2023.06.30
Download PDF
⟨ Previous Next ⟩

Abstract

Trifludimoxazin is a triazinone herbicide that inhibits the synthesis of protoporphyrinogen oxidase (PPO). The lack of PPO damages the cell membranes, leading to plant cell death. An official analytical method for the safety management of trifludimoxazin is necessary because it is a newly registered herbicide in Korea. Therefore, this study aimed to develop a residual analysis method to detect trifludimoxazin in five representative agricultural products. The EN method was established as the final extraction method by comparing the recovery test and matrix effect with those of the QuEChERS method. Various sorbent agents were used to establish the clean-up method, and no differences were observed among them. MgSO4 and PSA were selected as the final clean-up conditions. We used LC-MS/MS considering the selectivity and sensitivity of the target pesticide and analyzed the samples in the MRM mode. The recovery test results using the established analysis method and inter-laboratory validation showed a valid range of 73.5-100.7%, with a relative standard deviation and coefficient of variation less than 12.6% and 14.5%, respectively. Therefore, the presence of trifludimoxazin can be analyzed using a modified QuEChERS method, which is widely available in Korea to ensure the safety of residual insecticides.

Trifludimoxazin은 triazinone 계열 제초제로 프로토포르 피리노겐-IX 산화효소(protoporphyrinogen oxidase, PPO)를 억제하며 벼와 광엽 잡초를 방제하는 데 사용된다. PPO의 결핍은 세포막의 손상을 일으켜 식물을 시들게 한다. Trifludimoxazin의 농산물 중 잔류허용기준은 미국에서 아몬드에 대하여 0.15 mg/kg, 땅콩 등 9종에 대하여 0.01 mg/kg으로 설정되어있으며, 모화합물을 잔류물의 정의로 설정하여 관리하고 있다. 코덱스(CODEX), 유럽(EC) 일본(JFCRF)에서는 잔류허용기준(MRL)과 잔류물의 정의가 설정되어 있지 않다. 호주(APVMA)에서는 trifludimoxazin과 대사체 M850H001의 합을 잔류물의 정의로 설정하였으며, MRL은 보리와 밀에 0.01 mg/kg으로 설정되어 있다. 국내에서 신규 등록 예정임에 따라 본 연구에서는 농산물 중 trifludimoxazin의 잔류량을 분석하기 위한 공정시험법을 마련하고자 하였다. Trifludimoxazin의 물리 화학적 특성을 고려하여 아세토니트릴을 추출용매로 사용하는 Quick, easy, cheap, effective, rugged and safe (QuEChERS)법을 이용하여 추출 및 정제조건을 확립한 후 LC-MS/MS를 분석기기로 선정하였다. Trifludimoxazin의 결정계수(R2)는 모두 0.99 이상으로 우수하였으며 정량한계는 0.01 mg/kg으로 나타났다. 대표 농산물 5종(현미, 감자, 대두, 감귤, 고추)에 대하여 정량한계, 정량한계 10배, 정량한계 50배 수준으로 처리하여 회수율 실험을 한 결과 평균 회수율은(5반복) 73.5-85.3%로 나타났으며, 상대 표준편차(RSD)는 3.8% 이하로 나타났다. 본 연구는 국제식품규격위원회 농약 분석법 가이드라인의 잔류농약 분석 기준 및 식품의약품안전평가원의 식품등 시험법 마련 표준절차에 관한 가이드라인(2016)에 적합한 수준이며, 향후 공정시험법으로 활용될 예정이다. 본 연구에서 개발한 시험법에 대해 농산물 125건을 대상으로 잔류농약 모니터링을 한 결과 trifludimoxazin의 잔류량이 확인되지 않았다.

Keywords

Acknowledgement

본 연구는 2022년도 식품의약품안전평가원 "2022년 식품 중 잔류농약 안전관리를 위한 위해평가 및 신규 시험법 확립 연구(22191농축산316)"의 연구개발비 지원에 의해 수행되었으며, 이에 감사드립니다.

References

  1. Umetsu, N., Shirai, Y., Development of novel pesticides in the 21st century. J. Pes. Sci., 45, 55-74 (2020). https://doi.org/10.1584/jpestics.W20-05
  2. Tian, F., Qiao, C., Wang, C., Luo, J., Guo, L., Pang, T., Li, J., Wang, R., Pang, R., Xie, H., Development and validation of a method for the analysis of trifludimoxazin, picarbutrazox and pyraziflumid residues in cereals, vegetables and fruits using ultra-performance liquid chromatography/tandem mass spectrometry. Microchemical Journal, 168, 106477 (2021).
  3. Asher, B. S., Dotray, P. A., Liebl, R. A., Keeling, J. W., Ritchie, G. D., Udeigwe, T. K., Reed, J. D., Keller, K. E., Bowe, S. J., Aldridge, R. B., Simon, A., Vertical mobility and cotton tolerance to trifludimoxazin, a new protoporphyrinogen oxidase-inhibiting herbicide, in three West Texas soils. Weed Technology, 35, 144-148 (2021). https://doi.org/10.1017/wet.2020.95
  4. Yang, Y., Lin, G., Liu, L., Lin, T., Rapid determination of multi-antibiotic residues in honey based on modified QuEChERS method coupled with UPLC-MS/MS. Food Chem., 374, 131733 (2022).
  5. Wu, Y., An, Q., Li, D., Kang, L., Zhou, C., Zhang, J., Pan, C., Multi-residue analytical method development and risk assessment of 56 pesticides and their metabolites in tea by chromatography tandem mass spectroscopy. Food Chem., 375, 131819 (2022).
  6. Zhao, H., Zhao, Z., Li, X., Di, S., Qi, P., Wang, Z., Wang, J., Tian, P., Xu, H., Wang, X., Development of rapid low temperature assistant modified QuEChERS method for simultaneous determination of 107 pesticides and relevant metabolites in animal lipid. Food Chem., 395, 133606 (2022).
  7. Harischandra, N.R., Pallavi, M.S., Bheemanna, M., PavanKumar, K., Reddy, V.C.S., Udaykumar, N.R., Paramasivam, M. Yadav, S., Simultaneous determination of 79 pesticides in pigeonpea grains using GC-MS/MS and LC-MS/MS. Food Chem., 347, 128986 (2021).
  8. Naik, R.H., Pallavi, M.S., Kumar, K.P., Vanitha, B.K., Reddy, V.C.S., Shwetha, A., Nandini, S., Naveenkumar, P., Nidoni, R.U., Bheemanna, M., Determination of 72 chemical pesticides and estimation of measurement of uncertainty in rice using LC-MS/MS and GC-MS/MS. Food Analytical Methods, 14, 1788-1805 (2021).
  9. Melo, M.G., Carqueijo, A., Freitas, A., Barbosa, J., Silva, A. S., Modified QuEChERS extraction and HPLC-MS/MS for simultaneous determination of 155 pesticide residues in rice (Oryza sativa L.). Foods, 9, 1-16 (2020).
  10. Hu, M., Qiu, J., Zhang, H., Fan, X., Liu, K., Zeng, D., Tan, H., Method development and validation of indaziflam and its five metabolites in soil, water, and fruits by modified QuEChERS and UHPLC-MS/MS. J. Agr. Food Chem., 66, 10300- 10308 (2018). https://doi.org/10.1021/acs.jafc.8b04186
  11. Guo, Q., Zhao, S., Zhang, J., Qi, K., Du, Z., Shao, B., Determination of fipronil and its metabolites in chicken egg, muscle and cake by a modified QuEChERS method coupled with LC-MS/MS. Food Additives & Contaminants: Part A, 35, 1543-1552 (2018). https://doi.org/10.1080/19440049.2018.1472395
  12. Anastassiades, M., Lehotay, S.J., Stajnbaher, 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 Int., 86, 412-431 (2003). https://doi.org/10.1093/jaoac/86.2.412
  13. Wilkowska, A., Biziuk, M., Determination of pesticide residues in food matrices using the QuEChERS methodology. Food Chemistry, 125, 803-812 (2011). https://doi.org/10.1016/j.foodchem.2010.09.094
  14. Rejczak, T., Tuzimski, T., A review of recent developments and trends in the QuEChERS sample preparation approach. Open Chem., 13, 980-1010 (2015).
  15. Lehotay, S. J., Son, K. A., Kwon, H., Koesukwiwat, U., Fu, W., Mastovska, K., Hoh, E., Leepipatpiboon, N., Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. J. Chrom. A, 1217, 2548-2560 (2010). https://doi.org/10.1016/j.chroma.2010.01.044
  16. Lehotay, S. J., Mastovska, K., Lightfield, A. R., Use of buffering and other means to improve results of problematic pesticides in a fast and easy method for residue analysis of fruits and vegetables. J. AOAC Int., 88, 615-629 (2005). https://doi.org/10.1093/jaoac/88.2.615
  17. Moon, S. Y., Choi, H.J., Kim, S.R., Lee, K.H., Lee, S.G., Song, S.H., Lee, S.Y., Park, H.D., Recommendations for liquid chromatography-mass spectrometry in the clinical laboratory: Part II. Method validation. Laboratory Medicine Online, 10, 95-108 (2020).
  18. Ferrer, C., Lozano, A., Aguera, A., Giron, A. J., Fernandez-Alba, A. R., Overcoming matrix effects using the dilution approach in multiresidue methods for fruits and vegetables. J. Chrom. A, 1218, 7634-7639 (2011). https://doi.org/10.1016/j.chroma.2011.07.033
  19. Ministry of Food and Drug Safety (MFDS), (2023, May 24). Food Code. Retrieved from https://www.foodsafetykorea.go.kr/foodcode/01_03.jsp?idx=404
  20. CODEX Alimentarius Commission, Guidelines on good laboratory practice in residue analysis, CAC/GL 40-1993, Roma, Italy, 1-36 (2010).
  21. Ministry of Food and Drug Safety (MFDS), Guidelines on standard procedures for preparing analysis method (2016).