Journal of Food Hygiene and Safety (한국식품위생안전성학회지)

The Korean Society of Food Hygiene and Safety (한국식품위생안전성학회)
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Development and Validation of Analytical Method for Determination of Fungicide Spiroxamine Residue in Agricultural Commodities Using LC-MS/MS

LC-MS/MS를 이용한 농산물 중 살균제 Spiroxamine의 시험법 개발 및 검증

  • 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) ;
  • 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) ;
  • Lim, Seung-Hee (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, Ji-Hye (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Pak, Won-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) ;
  • Kuk, Ju-Hee (Nutrition and Functional Food Research Team, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Chung, Hyung-Wook (Pesticide and Veterinary Drug Residues Division, Food Safety Evaluation Department, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety)
  • 박신민 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 도정아 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 임승희 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 윤지혜 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 박원민 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 신혜선 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과) ;
  • 국주희 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 영양기능연구팀) ;
  • 정형욱 (식품의약품안전처 식품의약품안전평가원 식품위해평가부 잔류물질과)
  • Received : 2018.05.09
  • Accepted : 2018.07.11
  • Published : 2018.08.30
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Abstract

Spiroxamine, one of fungicides, is used to control powdery mildew in various crops and black yellow sigatoka in bananas. The major strength of spiroxamine is to control powdery mildew in various crops and bananas yellow sigatoka in bananas. The compound has shown a high level of activity, good persistence and crop tolerance. Besides powdery mildew, good control of rust, net blotch and Rhynchosporium diseases been indicated in cereals, together with a complementary activity against Septoria diseases. In 2017, the maximum residue limit (MRL) of spiroxamine established in Korea. According to Ministry of ood and rug afety) regulations, spiroxamine residues defined only parent compound. Thus, a analytical method is needed to estimate the residue level of the parent compound. The objective of this study was to develop and validate analytical method for spiroxamine in representative agricultural commodities. Samples were extracted with acetonitrile and partitioned with dichloromethane to remove the interfering substances. The analyte were quantified and confirmed liquid chromatograph-tandem mass spectrometer (LC-MS/MS) in positive-ion mode using multiple reaction monitoring (MRM). Matrix matched calibration curves were linear over the calibration ranges ($0.0005{\sim}0.1{\mu}g/mL$) for the analyte in blank extract with coefficient of determination ($r^2$) > 0.99. For validation purposes, recovery studies will be carried out at three different concentration levels (LOQ, 10LOQ, and 50LOQ) performing five replicates at each level. The recoveries 70.6~104.6% with relative standard deviations (RSDs) less than 10%. All values were consistent with the criteria ranges in the Codex guidelines (CAC/GL40, 2003) and MFDS guidelines. proposed analytical method be used as an official analytical method in the Republic of Korea.

본 연구는 농산물 중 2017년 기준신설예정농약 spiroxamine에 대한 공정시험법을 개발하고자 수행하였다. Spiroxamine은 모화합물만이 잔류물로 정의되므로 이를 분석하기 위한 시험법을 개발하였고, 확립된 시험법은 실험실 내 및 실험실 간 검증을 통해 공정시험법으로의 유효성을 확인하였다. Spiroxamine의 물리화학적 특성을 고려하여 분석을 위해 LC-MS/MS를 분석기기로 사용하였으며, acetonitrile으로 추출 후 유기용매를 이용하여 액액분배조건 및 florisil cartridge를 이용한 SPE 정제조건을 확립하여 시료의 불순물을 효과적으로 정제하는 시험법을 개발하였다. 개발된 Spiroxamine 시험법의 직선성은 결정계수($r^2$)가 0.99 이상으로 우수하였으며, 검출한계 및 정량한계는 각각 0.0005, 0.001 mg/kg으로 높은 감도를 나타내었다. 대표 농산물 5종(현미, 감자, 대두, 감귤, 고추)에 대한 시험법 검증결과 평균 회수율(5 반복)은 71.9~98.8%였고, 분석오차는 10.0% 이하로 정확성 및 재현성이 우수함을 확인할 수 있었다. 또한 광주지방식약청과의 실험실 간 검증 결과에서 평균 회수율은 70.6~104.6%를 나타내어 모두 Codex 가이드라인 및 식약처 가이드라인의 기준에 부합하는 것으로 확인되었다. 개발된 시험법은 낮은 검출한계 및 정량한계, 우수한 직선성, 회수율 시험을 통한 양호한 정밀성 및 재현성 등이 입증되어 농산물 중 Spiroxamine의 분석을 위한 식품공전 공정시험법으로 활용되기에 적합한 것으로 판단된다.

Keywords

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