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Development of an Analytical Method for the Determination of Pyriofenone residue in Agricultural Products using HPLC-UVD

HPLC-UVD를 이용한 농산물 중 살균제 pyriofenone 분석법 확립

  • Park, Hyejin (Pesticide and Veterinary Drug Residues Division, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Kim, HeeJung (Pesticide and Veterinary Drug Residues Division, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Do, Jung-Ah (Advanced Analysis Team, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Kwon, Ji-Eun (Pesticide and Veterinary Drug Residues Division, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Yoon, Ji-Young (Pesticide and Veterinary Drug Residues Division, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Lee, Ji-Young (Pesticide and Veterinary Drug Residues Division, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Chang, Moon-Ik (Pesticide and Veterinary Drug Residues Division, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Rhee, Gyu-Seek (Pesticide and Veterinary Drug Residues Division, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety)
  • 박혜진 (식품의약품안전처 식품의약품안전평가원 잔류물질과) ;
  • 김희정 (식품의약품안전처 식품의약품안전평가원 잔류물질과) ;
  • 도정아 (식품의약품안전처 식품의약품안전평가원 첨단분석팀) ;
  • 권지은 (식품의약품안전처 식품의약품안전평가원 잔류물질과) ;
  • 윤지영 (식품의약품안전처 식품의약품안전평가원 잔류물질과) ;
  • 이지영 (식품의약품안전처 식품의약품안전평가원 잔류물질과) ;
  • 장문익 (식품의약품안전처 식품의약품안전평가원 잔류물질과) ;
  • 이규식 (식품의약품안전처 식품의약품안전평가원 잔류물질과)
  • Received : 2014.03.19
  • Accepted : 2014.05.02
  • Published : 2014.06.30

Abstract

Pyriofenone is an aryl phenyl ketone fungicide that is newly registered in Korea in 2013 to control powdery mildew on food. The objective of this study was to develop reliable and sensitive analytical method for determination of pyriofenone residue in agricultural products for ensuring the food safety. The pyriofenone residues in all samples(Korean melon, pepper, potato, mandarin, soybean, and hulled rice) were extracted with acetonitrile, partitioned with dichloromethane, and then purified with a silica cartridge. The purified samples were analyzed by HPLC-UVD and confirmed with LC-MS. The linear range of pyriofenone was 0.05~5 mg/kg with the correlation coefficient ($r^2$) > 0.999. Average recoveries of pyriofenone ranged from 72.8% to 99.5% at the spiked level of 0.05 and 0.5 mg/kg, while the relative standard deviation was 2.3%~6.4%. In addition, the limit of detection and limit of quantification were 0.01 and 0.05 mg/kg, respectively. The results revealed that the developed and validated analytical method was suitable for pyriofenone determination in agricultural products.

피리오페논은 아릴페닐케톤계 농약으로, 식물 병원성 곰팡이의 부착 및 침투를 억제하여 방제 효과를 나타내는 살균제이다. 미국에서는 2012년에 피리오페논을 사용등록 하였으며, 우리나라에서는 2013년에 참외와 고추에 대해 잔류허용기준 설정을 추진하고 있다. 이에 따라, 본 연구에서는 식품 중 피리오페논의 안전관리를 위한 시험법을 개발하고자 하였다. 피리오페논은 분자량(365.8)이 크고 증기압이 $1.9{\times}10^{-6}Pa$ ($25^{\circ}C$)로 휘발성이 낮은 편으로, 질소, 산소원자의 비공유전자쌍과 이중결합이 UVD에 높은 감도를 보여 HPLC-UVD를 분석기기로 선택하였다. 추출용매는 물질의 용해도와 추출효율을 고려하여 acetonitrile로 선정하였으며, 피리오페논이 옥탄올/물 분배계수(logPow, $25^{\circ}C$)가 3.2인 비극성 물질이므로 증류수, 포화식염수와 dichloromethane을 사용하여 극성 불순물을 제거하도록 액-액 분배하였다. 분배 추출액을 silica 카트리지를 이용하여 정제하는데, hexane으로 세척한 후 hexane/acetone(90/10, v/v)로 용출하면 간섭 물질로부터 피리오페논을 효과적으로 정제할 수 있었다. 본 연구에서 확립한 시험법을 통한 대표작물에 대한 회수율은 72.8~99.5%이었고 분석오차는 10% 미만으로 코덱스 가이드라인((CAC/GL 40)에 적합하였다. LC-MS로 재확인 시험을 하여 시험법의 신뢰성과 선택성을 확보하였다. 본 연구에서 개발한 시험법은 식품 중 피리오페논의 안전관리를 위한 시험법으로 활용될 것이다.

Keywords

References

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