Korean Journal of Environmental Agriculture (한국환경농학회지)

The Korean Society of Environmental Agriculture (한국환경농학회)
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Establishment of Analytical Method for Dichlorprop Residues, a Plant Growth Regulator in Agricultural Commodities Using GC/ECD

GC/ECD를 이용한 농산물 중 생장조정제 dichlorprop 잔류 분석법 확립

  • Lee, Sang-Mok (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Kim, Jae-Young (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Kim, Tae-Hoon (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Lee, Han-Jin (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Chang, Moon-Ik (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Kim, Hee-Jeong (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Cho, Yoon-Jae (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Choi, Si-Won (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Kim, Myung-Ae (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Kim, MeeKyung (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Rhee, Gyu-Seek (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety) ;
  • Lee, Sang-Jae (Pesticide and Veterinary Drug Residues Division, Department of Food Safety Evaluation, National Institute of Food and Drug Safety Evaluation, Ministry of Food and Drug Safety)
  • 이상목 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 김재영 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 김태훈 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 이한진 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 장문익 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 김희정 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 조윤제 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 최시원 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 김명애 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 김미경 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 이규식 (식품의약품안전처 식품의약품안전평가원 식품위해평가부) ;
  • 이상재 (식품의약품안전처 식품의약품안전평가원 식품위해평가부)
  • Received : 2013.07.23
  • Accepted : 2013.08.21
  • Published : 2013.09.30
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Abstract

BACKGROUND: This study focused on the development of an analytical method about dichlorprop (DCPP; 2-(2,4-dichlorophenoxy)propionic acid) which is a plant growth regulator, a synthetic auxin for agricultural commodities. DCPP prevents falling of fruits during their growth periods. However, the overdose of DCPP caused the unwanted maturing time and reduce the safe storage period. If we take fruits with exceeding maximum residue limits, it could be harmful. Therefore, this study presented the analytical method of DCPP in agricultural commodities for the nation-wide pesticide residues monitoring program of the Ministry of Food and Drug Safety. METHODS AND RESULTS: We adopted the analytical method for DCPP in agricultural commodities by gas chromatograph in cooperated with Electron Capture Detector(ECD). Sample extraction and purification by ion-associated partition method were applied, then quantitation was done by GC/ECD with DB-17, a moderate polarity column under the temperature-rising condition with nitrogen as a carrier gas and split-less mode. Standard calibration curve presented linearity with the correlation coefficient ($r^2$) > 0.9998, analysed from 0.1 to 2.0 mg/L concentration. Limit of quantitation in agricultural commodities represents 0.05 mg/kg, and average recoveries ranged from 78.8 to 102.2%. The repeatability of measurements expressed as coefficient of variation (CV %) was less than 9.5% in 0.05, 0.10, and 0.50 mg/kg. CONCLUSION(S): Our newly improved analytical method for DCPP residues in agricultural commodities was applicable to the nation-wide pesticide residues monitoring program with the acceptable level of sensitivity, repeatability and reproducibility.

Dichlorprop(DCPP)는 phenoxyalkanoic acid계열로서 인체에 유해한 것으로 알려진 fenoprop, 2,4-D 및 daminozide의 대체 약제로 사용되어온 auxin 활성 생장조정제로 과수의 낙과 방지에 이용된다. 하지만, DCPP의 과다 사용은 과실의 숙기를 촉진시키며 연화 및 저장력을 현저히 저하하는 부정적인 영향을 나타내며, 제초제의 특성을 나타내기 때문에 농산물에 과다 사용하여 잔류허용기준을 초과할 경우, 인체에 유해할 수 있다. 따라서 본 연구는 생장조정제로 사용되고 있는 DCPP에 대하여 국내에 유통되는 농산물을 대상으로 잔류 실태 조사 연구를 실시하고자 기존 식품공전 분석법을 개선하여 신속하고 효율적인 분석법으로 재확립 하였다. 분석법 검증에 사용된 시료는 농산물의 메트릭스를 대표할 수 있는 농산물 5종(감귤, 감자, 고추, 대두 및 현미)을 사용하였다. 검체에 아세톤을 가하고 산성화시켜 추출한 후 산-염기 액-액 분배법을 이용해 추출, 정제 및 농축 과정을 거쳤다. 농축에 의해 얻어진 잔류물은 메탄올로 재용해한 후, 이중 2 mL를 취해 $BF_3$-메탄올 용액으로 메틸화한 후, 헥산 및 5% 염화나트륨을 사용해 최종 정제를 거친 용액을 헥산으로 재용해하여 GC/ECD에 주입하였다. 기기분석은 DB-17 중간 극성 칼럼과 운반 기체로 질소 가스를 사용하였고, split-less 모드 하에 $1{\mu}L$를 주입하여 승온 조건으로 ECD에 의해 측정하였다. 또한, GC/MS를 통해 확인시험을 수행 하였으며, 모든 검증은 CAC 가이드라인(CAC/GL 40, 1993) 규정에 따라 실시하였다. 그 결과, DCPP의 정량 한계는 모든 검체에서 0.05 mg/kg 수준이었고, 회수율은 감귤89.5-94.3%, 감자 79.4-87.4%, 고추 90.5-102.2%, 대두 78.8-101.1%, 현미 90.5-100.4%였으며, 변동계수는 감귤 2.5-9.5%, 감자 1.4-2.6%, 고추 2.7-3.9%, 대두 3.4-7.3%, 현 미 1.2-2.1%로 나타났다. 이상의 결과는 국제식품규격위원회 가이드라인 규정(CAC/GL 40, 1993)에 만족하는 수준으로, 새롭게 개선된 DCPP 분석법은 향후 국내 유통 농산물을 대상으로 한 생장조정제 DCPP의 잔류 실태 조사 연구에 활용될 계획이다.

Keywords

References

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