수출입 농산물의 잔류농약 검사를 위한 유기인계 농약 8종의 동시 분석

국문 초록 (Abstract)

본 연구에서는 농산물 시료 중 GC-NPD/MS 분석법을 이용하여 물리화학적 특성이 유사한 유기인계 살충제 chlorpyrifosmethyl, mecarbam, parathion-methyl, phenthoate, prothiofos, tebupirimfos, 유기인계 살균제 iprobenfos 및 유기인계 제초제 anilofos를 포함하는 8종의 유기인계 농약에 대해 동시 분석법을 확립하였다. 농산물 시료에 acetone을 가하여 추출된 대상 농약 8종의 잔류분은 n-hexane 분배법과 florisil 흡착 크로마토그래피법으로 정제하여 분석대상 시료로 하였다. DB-17 capillary column을 이용한 GC-NPD 분석 시 불순물의 간섭은 없었으며, 감귤, 고추, 배추, 현미 및 콩을 포함한 5종의 대표 농산물 중 대상농약 8종 각각의 정량한계(LOQ)는 tebupirimfos, chlorpyrifos-methyl 및 parathion-methyl은 0.004 mg/kg, 그 외 iprobenfos, mecarbam, prothiofos, phenthoate 및 anilofos는 0.008 mg/kg이었다. 5종의 대표 농산물에 대한 대상농약 전체의 회수율은 80.5~105.0%를 나타내었으며, 농산물 시료 및 처리수준에 관계없이 10% 미만의 분석오차를 나타내어 잔류분석기준 이내를 만족하였다. 본 연구에서 확립된 유기인계 농약 8종(anilofos, chlorpyrifos-methyl, iprobenfos, mecarbam, parathion-methyl, phenthoate, prothiofos 및 tebupirimfos)의 동시 분석법은 검출한계, 회수율 및 분 석오차 면에서 국제적 분석기준을 만족할 뿐만 아니라, GC/ MS SIM을 이용한 잔류분의 재확인 과정의 결과를 종합해 볼 때 분석과정의 편이성 및 신뢰성이 확보된 계열별 동시 분석법으로 국내·외 수출입 농산물 잔류농약 검사에 사용 가능할 것이다.

다국어 초록 (Multilingual Abstract)

This experiment was conducted to establish a simultaneous analytical method for 8 kinds of organophosphorus pesticides of 3 different purposes with similar physicochemical characteristics as insecticide(chlorpyrifos-methyl, mecarbam, parathion- methyl, phenthoate, prothiofos and tebupirimfos), fungicide(iprobenfos), and herbicide (anilofos) in crops using GC-NPD/MS. All the pesticides residues were extracted with acetone from representative samples of five raw products which comprised mandarin, green pepper, kimchi cabbage, hulled rice and soybean. The extract was diluted with large volume of saline water and directly partitioned into n-hexane to remove polar co-extractives in the aqueous phase. For the hulled rice and soybean samples, n-hexane/ acetonitrile partition was additionally employed to remove non-polar lipids. The extract was finally purified by optimized florisil column chromatography. The analytes were separated and quantitated by GLC with NPD using a DB-17 capillary column. Accuracy and precision of the proposed method was validated by the recovery experiment on every crop samples fortified with anilofos, chlorpyrifos-methyl, iprobenfos, mecarbam, parathion-methyl, phenthoate, prothiofos and tebupirimfos at 3 concentration levels per crop in each triplication. Mean recoveries ranged from 80.5 to 105.0% in five representative agricultural commodities. The coefficients of variation were all less than 10%, irrespective of sample types and fortification levels. Limit of quantitation(LOQ) of the analytes were 0.004(tebupirimfos, chlorpyrifos-methyl and parathion-methyl) and 0.008(iprobenfos, mecarbam, prothiofos, phenthoate and anilofos) mg/kg as verified by the recovery experiment. A confirmatory technique using GC/MS with selected-ion monitoring was also provided to clearly identify the suspected residues. Therefore, this analytical method was reproducible and sensitive enough to determine the residues of anilofos, chlorpyrifos-methyl, iprobenfos, mecarbam, parathion-methyl, phenthoate, prothiofos, and tebupirimfos in import-export agricultural products.

목차 (Table of Contents)

• ABSTRACT
• 서 언
• 재료 및 방법
• 시약 및 기구
• 농산물 시료
• GC-NPD/MS 기기분석 조건
• 표준검량선 및 분석정량한계(Limit of quantitation, LOQ)
• 시료 추출 및 분배
• Florisil 흡착크로마토그래피
• 대표 농산물에 대한 유기인계 농약 8종의 회수율 검정
• 결과 및 고찰
• GC-NPD 분석조건의 확립
• 시료 추출 및 분배과정의 확립
• Florisil 흡착 크로마토그래피 정제조건의 최적화
• 농산물 시료 중 유기인계 농약 8종의 분석정량한계 및 회수율
• GC/MS를 이용한 잔류분의 재확인
• 적 요
• REFERENCES

참고문헌 (Reference)

1 이재윤, "유통 친환경 과실류와 과채류 중 농약잔류 실태조사 및 안전성 평가" 한국농약과학회 16 (16): 308-314, 2012

2 이종화, "시설 내 오이 재배 중 살균제 Boscalid의 잔류특성" 한국농약과학회 12 (12): 67-73, 2008

3 심혜림, "고감도 및 고선택성의 유기인계/카바메이트계 농약 검출용 바이오칩 센서" 한국공업화학회 20 (20): 571-580, 2009

4 Pang, G. F., "Validation study on 660 pesticide residues in animal tissues by gel permeation chromatography cleanup/gas chromatography-tandem mass spectrometry" 1125 : 1-30, 2006

5 Qin, Y., "The comparison of dispersive solid phase extraction and multi-plug filtration cleanup method based on multi-walled carbon nanotubes for pesticides multi-residue analysis by liquid chromatography tandem mass spectrometry" 1385 : 1-11, 2015

6 Rural Development Adminstration, "Safety and Crop protection of pesticide" 1-11, 2000

7 United States Environmental Protection Agency, "Report on FQPA tolerance reassessment progress and interim risk management decision for phostebupirim" 6-7, 2006

8 Sivaperumal, P., "Rapid determination of pesticide residues in fruits and vegetables, using ultra-high-performance liquid chromatography/time- of-flight mass spectrometry" 168 : 356-365, 2015

9 AOAC, "Pesticide and industrial chemical residues, In official method of analysis"

10 Lee, Y. D., "Pesticide analytical residues manual in food code"

11 Fong, W.G, "Pesticide Residues in Food: Methods, Technologies and Regulations"

12 US Food and Drug Administration, "Pesticide Analytical Manual, Vol 1: Multi-residue Methods" 1999

13 Canada. Hayward, D.G., "Multiresidue pesticide analysis of botanical dietary supplements using salt-out acetonitrile extraction, solid-phase extraction cleanup column, and gas chromatography-triple quadrupole mass spectrometry" 85 (85): 4686-4693, 2013

14 He, Z., "Multiresidue analysis of over 200 pesticides in cereals using a QuEChERS and gas chromatography-tandem mass spectrometrybased method" 169 : 372-380, 2015

15 Wang, S., "Multi-residue determination of pesticides in water using multi-walled carbon nanotubes solid-phase extraction and gas chromatography-mass spectrometry" 1165 : 166-171, 2007

16 Cha, K. S., "Monitoring of pesticide residues in commercial medicinal herbs in Busan(II)" 22 (22): 57-71, 2012

17 Roberts, T., "Metabolic pathways of agrochemicals:part two–insecticides and fungicides" Royal Society of Chemistry 1999

18 Ministry of Food and Drug Safety, "MRLs for pesticides in foods"

19 Ministry of Food and Drug Safety, "Korea Food Code"

20 European Commission, "Identify, physical and chemical properties for chlorpyrifos- methyl"

21 Codex Alimentarius Commission, "Guidelines on Good Laboratory Practice in Residue Analysis. CAC/GL 40-1993, Rev.1-2003"

22 California Environmental Protection Agency, "Evaluation of methyl parathion as a toxic air contaminant" 2-, 1999

23 López, M. G., "Evaluation and validation of an accurate mass screening method for the analysis of pesticides in fruits and vegetables using liquid chromatography-quadrupole-time of flightmass spectrometry with automated detection" 1373 : 40-50, 2014

24 Lee, M. G, "Estimation of cumulative dietary risk of pesticides sharing acetyl- colinesterase inhibitory effects" 12 (12): 43-50, 2003

25 Janssen, M. M. T., "Contaminants, in food safety and toxity" CRC Press 58-56, 1997

26 Miller, J. M, "Chromatography : Concepts and contrasts" 286-287, 2005

27 United States Environmental Protection Agency, "Chlorpyrifos-methyl Facts"