Journal of Food Hygiene and Safety (한국식품위생안전성학회지)

The Korean Society of Food Hygiene and Safety (한국식품위생안전성학회)
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Development of a Simultaneous Analytical Method for Determination of Insecticide Broflanilide and Its Metabolite Residues in Agricultural Products Using LC-MS/MS

LC-MS/MS를 이용한 농산물 중 살충제 Broflanilide 및 대사물질 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) ;
  • Park, Shin-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) ;
  • 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) ;
  • Kim, Ji-Young (Division of Import Food Analysis, Ministry of Food and Drug Safety-Seoul Region, 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) ;
  • 박신민 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 조성민 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 김지영 (식품의약품안전처 서울지방식품의약품안전청 수입식품분석과) ;
  • 신혜선 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 장동은 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 정용현 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 이강봉 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과)
  • Received : 2019.02.08
  • Accepted : 2019.03.13
  • Published : 2019.04.30
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Abstract

An analytical method was developed for the determination of broflanilide and its metabolites in agricultural products. Sample preparation was conducted using the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method and LC-MS/MS (liquid chromatograph-tandem mass spectrometer). The analytes were extracted with acetonitrile and cleaned up using d-SPE (dispersive solid phase extraction) sorbents such as anhydrous magnesium sulfate, primary secondary amine (PSA) and octadecyl ($C_{18}$). The limit of detection (LOD) and quantification (LOQ) were 0.004 and 0.01 mg/kg, respectively. The recovery results for broflanilide, DM-8007 and S(PFP-OH)-8007 ranged between 90.7 to 113.7%, 88.2 to 109.7% and 79.8 to 97.8% at different concentration levels (LOQ, 10LOQ, 50LOQ) with relative standard deviation (RSD) less than 8.8%. The inter-laboratory study recovery results for broflanilide and DM-8007 and S (PFP-OH)-8007 ranged between 86.3 to 109.1%, 87.8 to 109.7% and 78.8 to 102.1%, and RSD values were also below 21%. All values were consistent with the criteria ranges requested in the Codex guidelines (CAC/GL 40-1993, 2003) and the Food and Drug Safety Evaluation guidelines (2016). Therefore, the proposed analytical method was accurate, effective and sensitive for broflanilide determination in agricultural commodities.

본 연구는 농산물 중 2019년 기준신설 예정농약 Broflanilide에 대한 공정시험법을 개발하고자 수행하였다. Broflanilide는 meta-diamide계 살충제로 중추신경계 억제성 신경전달물질인 gamma-aminobutyric acid (GABA) 수용체에 대하여 비경쟁적으로 작용하여 해충을 마비시키는 강한 살충작용을 하고 담배거세미나방 방제에 효과적이다. 잔류물의 정의는 모화합물 broflanilide로 규정하여 관리할 예정으로 향후 대사산물의 안전관리를 고려하여 broflanilide 및 대사산물의 동시시험법을 확립하고자 하였다. 아세토니트릴으로 추출 후 무수황산마그네슘 및 염화나트륨을 첨가하였고 원심분리하였다. 상등액을 취하여 PSA와 $C_{18}$ 흡착제를 사용해 간섭물질을 효과적으로 제거한 후 LC-MS/MS로 분석하는 시험법을 개발하였다. 개발된 broflanilide 시험법의 직선성은 결정계수($r^2$)가 0.99 이상으로 우수하였으며, 검출한계 및 정량한계는 각각 0.004, 0.01 mg/kg으로 높은 감도를 나타내었다. 대표 농산물 5품목(현미, 감자, 대두, 감귤, 고추)에 대하여 시험법 검증결과 평균 회수율(5반복)은 broflanilide는 90.7~113.7%, DM-8007은 88.2~105.0%, S(PFP-OH)-8007은 79.8~97.8%이었으며 RSD는 8.8% 이하로 정확성 및 반복성이 우수함을 확인할 수 있었다. 또한 외부실험기관인 서울지방식약청과의 실험실간 평균 회수율은 broflanilide의 경우 86.3~109.1%, DM-8007은 87.8~109.7%, S(PFP-OH)-8007은 78.8~102.1%으로 상대표준편차(RSD)는 모두 20.8%이하로 국제식품규격위원회 가이드라인(Codex Alimentarius Commission, CAC/GL 40-1993, 2003)의 잔류농약 분석 기준 및 식품의 약품안전평가원의 '식품등 시험법 마련 표준절차에 관한 가이드라인(2016)'에 적합한 수준임을 확인하였다. 개발된 시험법은 낮은 검출한계 및 정량한계, 우수한 직선성, 회수율 실험을 통한 정확성과 정밀성, 재현성 등이 입증되어 농산물 중 broflanilide의 잔류검사를 위한 공정시험법으로 활용되기에 적합한 것으로 판단된다.

Keywords

References

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