Journal of Food Hygiene and Safety (한국식품위생안전성학회지)

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

DOI QR Code

Improvement of an Analytical Method for Methoprene in Livestock Products using LC-MS/MS

LC-MS/MS를 이용한 축산물 중 살충제 메토프렌의 잔류분석법 개선

  • Park, Eun-Ji (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, Nam Young (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Park, So-Ra (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, Jung Mi (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) ;
  • Yoon, Hae Jung (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety)
  • 박은지 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 김남영 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 박소라 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 이정미 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 정용현 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 윤혜정 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과)
  • Received : 2022.05.06
  • Accepted : 2022.05.26
  • Published : 2022.06.30
Download PDF
⟨ Previous Next ⟩

Abstract

The research aims to develop a rapid and easy analytical method for methoprene using liquid chromatography-tandem mass spectrometry (LC-MS/MS). A simple, highly sensitive, and specific analytical method for the determination of methoprene in livestock products (beef, pork, chicken, milk, eggs, and fat) was developed. Methoprene was effectively extracted with 1% acetic acid in acetonitrile and acetone (1:1), followed by the addition of anhydrous magnesium sulfate (MgSO4) and anhydrous sodium acetate. Subsequently, the lipids in the livestock sample were extracted by freezing them at -20℃. The extracts were cleaned using MgSO4, primary secondary amine (PSA), and octadecyl (C18), which were then centrifuged to separate the supernatant. Nitrogen gas was used to evaporate the supernatant, which was then dissolved in methanol. The matrix-matched calibration curves were constructed using 8 levels (1, 2.5, 5, 10, 25, 50, 100, 150 ng/mL) and the coefficient of determination (R2) was above 0.9964. Average recoveries spiked at three levels (0.01, 0.1, and 0.5 mg/kg), and ranged from 79.5-105.1%, with relative standard deviations (RSDs) smaller than 14.2%, as required by the Codex guideline (CODEX CAC/GL 40). This study could be useful for residue safety management in livestock products.

메토프렌은 살충제로 곤충의 성장을 방해하는 유충호르몬 유사체로 널리 사용되고 있다. 국내 축산물에 대한 MRL은 0.05-0.1 mg/kg 수준으로 설정되어 있지만 PLS제도가 축산물을 대상으로 확대될 수 있기 때문에 0.01 mg/kg 이하에서 정량이 가능한 시험법이 필요하다. 기존의 식품공전에 존재하던 시험법(식품의약품안전처 공고 제 2021-69호, '21.8.9.)은 우유와 그 외 축산물의 전처리 과정이 서로 상이할 뿐 아니라 충전칼럼을 사용하여 노후화되고 복잡하다는 단점이 있다. 본 연구에서는 비교적 간편하며 분석 시간이 적게 소요되는 QuEChERS법을 활용하여 0.01 mg/kg의 정량한계를 만족하는 메토프렌 시험법을 마련하고자 하였다. 메토프렌의 물리·화학적 특성을 고려하여 1% 아세트산을 함유한 아세토니트릴:아세톤(1:1) 혼합액을 이용하여 진탕 추출 후 d-SPE를 이용한 정제조건을 확립하여 LC-MS/MS를 이용한 시험법을 개발하였다. 메토프렌의 결정계수(R2)는 0.99 이상으로 높은 직선성을 보여주었고, 정량한계는 0.01 mg/kg으로 높은 감도를 나타내었다. 대표 축산물 6종(소고기, 돼지고기, 닭고기, 우유, 계란, 지방)에 대하여 정량한계, 정량한계 10배, 정량한계 50배 수준으로 처리한 다음 회수율 실험을 한 결과 평균 회수율이 79.5-105.1%이었으며 상대표준편차는 14.2% 이하로 확인되었다. 본 연구는 국제식품규격위원회 가이드라인(Codex Alimentarius Commission, CAC/GL40)의 잔류농약 분석 기준 및 식품의약품안전평가원의 '식품등 시험법 마련 표준절차에 관한 가이드라인(2016)'에 적합한 수준임을 확인하였다. 따라서 본 연구에서 개발한 시험법은 추후 교차검증을 거쳐 축산물 중 잔류할 수 있는 메토프렌의 안전관리를 위한 공정시험법으로 활용 가능할 것이다.

Keywords

Acknowledgement

This study was supported by the Ministry of Food and Drug Safety, Republic of Korea (grant number: 20161농축산604).

References

  1. LeDoux, M., Analytical methods applied to the determination of pesticide residues in foods of anmal origin. A review of the past two decades. J. Chromatogr. A., 1218, 1021-1036 (2011). https://doi.org/10.1016/j.chroma.2010.12.097
  2. Chanbang, Y., Arthur, F.H., Wilde, G.E., Throne, J.E., Subramanyam, B.H., Susceptibility of eggs and adult fecundity of the lesser grain borer, Rhyzopertha dominica, exposed to methoprene. J. Insect Sci., 8, 48 (2008).
  3. Wijayaratne, L.K.W., Arthur, F.H., Whyard, S., Methoprene and control of stored-product insects. J. Stored Prod. Res., 76, 161-169 (2018). https://doi.org/10.1016/j.jspr.2016.09.001
  4. Hu, X.L., Niu, J.J., Meng, Q., Chai, Y.G., Chu, K.H., Chan, K.M., Effects of two juvenile hormone analogue insecticides, fenoxycarb and methoprene on Neocardina davidi. Environ. Pollut., 253, 89-99 (2019). https://doi.org/10.1016/j.envpol.2019.06.120
  5. Pubchem, Methoprene. Retrieved from https://pubchem.ncbi.nlm.nih.gov/compound/5366546
  6. CODEX, Pesticide Residue in Food and Feed. Retrieved from https://www.fao.org/fao-who-codexalimentarius/codex-texts/dbs/pestres/pesticide-detail/en/?p_id=147
  7. EU (European Commission), Pesticide database. Retrieved from https://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/mrls/?event=details&pest_res_ids=338&product_ids=&v=1&e=search.pr
  8. Canada, Pesticide database. Retrieved from http://oasdmz01.hc-sc.gc.ca/mrl-lrm/index-eng.php.
  9. Japan, The Japan Food Chemical Research Foundation. Retrieved from http://db.ffcr.or.jp/front/pesticide_detail?id=76100
  10. Ministry of Food and Drug Safety (MFDS), MRLs for Pesticide in Foods. Retrieved from https://www.foodsafetykorea.go.kr/foodcode/02_01_01.jsp?pesticide_code=P00042&s_option=EN&s_type=12
  11. Gary B.Q., Luana E.S., David A.S., Environmental degradation of the insect growth regulator methoprene (Isopropyl(2E,4E)-11-Methoxy-3,7,11-trimethyl-2,4-dodecadienoate).I.metabolism by alfalfa and rice. J. Agri. Food Chem., 22(4), 582-589 (1974). https://doi.org/10.1021/jf60194a022
  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. Lehotay, S.J., Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaborative study. J. AOAC Int., 90, 485-520 (2007). https://doi.org/10.1093/jaoac/90.2.485
  14. Lehotay, S.J., Son, K.A., Kwon, H., Koesukwiwat, U., Fu, W., Mastovska, K., Hoh, E., Leepipatpiboonc, N., Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. J. Chromatogr. A., 1217, 2548-2560 (2010). https://doi.org/10.1016/j.chroma.2010.01.044
  15. Li, S., Yu, P., Zhou, C., Tong, L., lI, D., Yu, Z., Zhao, Y., Analysis of pesticide residues in commercially available chenpi using a modified QuEChERS method and GC-MS/MS determination. J. Phanarm. Anal., 10, 60-69 (2020). https://doi.org/10.1016/j.jpha.2019.01.005
  16. Han L., Sapozhnikova Y., Lehotay S.J., Method validation for 243 pesticides and environmental contaminants in meats and poultry by tandem mass spectrometry coupled to lowpressure gas chromatography and ultrahigh-performance liquid chromatography. Food Control., 66, 270-282 (2016). https://doi.org/10.1016/j.foodcont.2016.02.019
  17. Choi, S., Kim, S., Shin, J.Y., Kim, M.K., Kim, J.H., Development and verification for analysis of pesticides in eggs and egg products using QuEChERS and LC-MS/MS. Food Chem., 173, 1236-1242 (2015). https://doi.org/10.1016/j.foodchem.2014.10.143
  18. Codex Alimentarius Commission, Guidelines on good laboratory practice in residue analysis (2003).
  19. Ministry of Food and Drug Safety, Guidelines on standard procedures for preparing analysis method (2016).
  20. 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
  21. Wilkowska, A., Biziuk, M., Determination of pesticide residues in food matrices using the QuEChERS methodology. Food Chem., 125, 803-812 (2011). https://doi.org/10.1016/j.foodchem.2010.09.094