GC-ECD/MS를 이용한 농산물 중 Bifenox, Ethalfluralin, Metolachlor, Oxyfluorfen, Pretilachlor, Thenylchlor 및 Trifluralin의 동시 분석

안경근 ( Kyung Geun Ahn ),김기쁨 ( Gi Ppeum Kim ),황영선 ( Young Sun Hwang ),강인규 ( In Kyu Kang ),이영득 ( Young Deuk Lee ),정명근 ( Myoung Gun Choung ) 한국환경농학회 2018 한국환경농학회지 Vol.37 No.2

본 연구는 GC-ECD/MS 분석법을 이용하여 농산물 시료 중 dinitroaniline계 제초제 ethalfluralin 및 trifluralin, chloroacetamide계 제초제 metolachlor, pretilachlor 및 thenylchlor와 diphenyl ether계 제초제 bifenox 및 oxfluorfen의 계역별 동시 분석법을 확립하였다. 농산물 시료에 acetone을 가하여 추출된 대상농약 7종의 잔류분은 n-hexane/dichloromethane(80/20, v/v)을 이용한 분배와 Florisil 흡착 크로마토그래피법으로 정제하여 분석대상 시료로 하였다. DB-1 capillary column을 이용한 GC-ECD 분석 시 불순물의 간섭은 없었으며, 사과, 고추, 배추, 현미 및 콩을 포함한 5종의 대표 농산물 중 대상농약 7종의 정량한계(LOQ)는 bifenox 0.02, ethalfluralin 0.004, metolachlor 0.008, oxyfluorfen 0.002, pretilachlor 0.008, thenylchlor 0.006 및 trifluralin 0.004 mg/kg이었다. 5종의 대표 농산물에 대한 대상농약 전체의 회수율은 75.7∼114.8%였으며, 농산물 시료 및 처리수준에 관계없이 10% 미만의 분석오차를 나타내어 잔류분석기준 이내를 만족하였다. 본 연구에서 확립된 7종의 제초제 성분인 bifenox, ethalfluralin, metolachlor, oxyfluorfen, pretilachlor, thenylchlor 및 trifluralin의 계열별 동시 분석법은 검출한계, 회수율 및 분석오차 면에서 국제적 분석기준을 만족할 뿐만 아니라, GC/MS SIM을 이용한 잔류분의 재확인 과정의 결과를 종합해 볼 때 분석과정의 편리성 및 신뢰성이 확보된 계열별 동시 분석법으로 사용이 가능할 것으로 판단된다. BACKGROUND: This experiment was conducted to establish a simultaneous analysis method for 7 kinds of herbicides in 3 different classes having similar physicochemical property as diphenyl ether(bifenox and oxyfluorfen), dinitroaniline (ethalfluralin and trifluralin), and chloroacetamide (metolachlor, pretilachlor, and thenylchlor) in crops using GC-ECD/MS. METHODS AND RESULTS: All the 7 pesticide residues were extracted with acetone from representative samples of five raw products which comprised apple, green pepper, Kimchi cabbage, hulled rice and soybean. The extract was diluted with saline water and directly partitioned into n-hexane/dichloromethane(80/20, v/v) 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 ECD using a DB-1 capillary column. Accuracy and precision of the proposed method was validated by the recovery experiment on every crop samples fortified with bifenox, ethalfluralin, metolachlor, oxyfluorfen, pretilachlor, thenylchlor, and trifluralin at 3 concentration levels per crop in each triplication. CONCLUSION: Mean recoveries of the 7 pesticide residues ranged from 75.7 to 114.8% 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 (etahlfluralin and trifluralin), 0.008 (metolachlor and pretilachlor), 0.006 (thenylchlor), 0.002 (oxyfluorfen), and 0.02 (bifenox) 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 bifenox, ethalfluralin, metolachlor, oxyfluorfen, pretilachlor, thenylchlor, and trifluralin in agricultural commodities.

06 식품의약품안전처 SESSION : GC-NPD/MS를 이용한 농산물 중 유기인계 농약의 동시분석법 확립

안경근 ( Kyung Geun Ahn ),김경하 ( Gyeong Ha Kim ),김기쁨 ( Gi Ppeum Kim ),김민지 ( Min Ji Kim ),김슬아 ( Seula Kim ),강련웅 ( Ryeon Woong Kang ),김정은 ( Jeong Un Kim ),황영선 ( Young Sun Hwang ),이영득 ( Young Deuk Lee ),정명근 한국환경농학회 2014 한국환경농학회 학술대회집 Vol.2014 No.-

본 연구는 유기인계 농약 중 제초제 anilofos, 살균제 iprobenfos, 살충제인 chlorpyrifos-methyl,mecarbam, parathion-methyl, phenthoate, prothiofos 및 tebupirimfos 등 8종 농약의 동시분석법을 개발하고자 하였다. 현재 식품공전에 수록되어 있는 이들 각 농약의 기기분석법은 GC-ECD,GC-NPD 혹은 GC-FPD 분석법이 각각 적용되어 있으므로 고감도 선택성 검출기의 적용이 필요하며, 아울러 기존 분석법은 packed column의 사용 및 cartridge 정제에 의해 정제도 및 재현성 불량 등 일상분석에 어려움이 있으므로, 본 연구는 농축, 유지제거 과정 및 정제과정의 간소화를 통해 보다 편리하고, 신뢰성 높은 GC-NPD/MS 분석법을 확립하고자 하였다. 부류별 5종(현미, 콩, 배추, 감귤 및 고추)의 대표 농산물을 선정하여 마쇄 후 아세톤으로 추출하고, 포화식염수와 증류수를 첨가한 뒤 n-hexane으로 액-액 분배하여 florisil 흡착크로마토그래피법으로 정제하였다. Florisil 정제법은 50 mL의 n-hexane/acetone(99.5:0.5, v/v)으로 세척한 후 150 mL의 n-hexane/ acetone (97:3, v/v)로 용출하여 chlorpyrifos-methyl, mecarbam, parathion-methyl, phenthoate, prothiofos 및 tebupirimfos의 6성분을 분리하였고, 추가적으로 150 mL의 n-hexane/acetone(92:8, v/v)로 anilofos 및 iprobenfos 2성분을 용출하였다. 분석대상 농약의 기기분석 시 resolution을 고려하여 최적의 분석용 GC 컬럼은 DB-17 capillary column으로 선정하였으며, 3수준 3반복으로 실험을 수행한 결과, 정량한계는 chlorpyrifos-methyl, parathion-methyl 및 tebupirimfos이 0.004 mg/kg, 그외 anilofos, iprobenfos, mecarbam, phenthoate 및 prothiofos는 0.008 mg/kg이었다. 각 대표 농산물에 대해 정량한계, 정량한계 10배 및 50배 수준에서 회수율을 검정한 결과, 모든 처리농도에서 80.7-105.0%의 회수율을 나타내었으며, 반복 간 변이계수(CV)는 최대 5.8% 미만으로 잔류분석 기준인 회수율 70-120% 및 분석오차 10% 이내를 만족하였다. 또한 GC/MS를 통해 잔류분을 재확인 하였으며, TIC(Total-Ion Chromatogram)와 mass spectrum을 고려하여 SIM (Selected-Ion Monitoring)을 통해 실제 농산물 시료에 적용하여 재확인 하였다. 이상의 결과로서 GC-NPD/MS를 이용한 유기인계 농약 anilofos, iprobenfos, chlorpyrifos-methyl, mecarbam, parathion-methyl, phenthoate, prothiofos 및 tebupirimfos의 동시분석법은 재현성 및 신뢰성이 확보된 정밀 분석법으로써, 일상적잔류 농약분석에 적용 가능할 것으로 판단된다.

식품의약품안전처 SESSION : GC/ECD/MS를 이용한 농산물 중 Quintozene의 잔류분석

안경근 ( Kyung Geun Ahn ),김기쁨 ( Gi Ppeum Kim ),조영욱 ( Young Wook Cho ),황영선 ( Young Sun Hwang ),이수진 ( Su Jin Lee ),윤원갑 ( Won Kap Yun ),강민주 ( Min Ju Kang ),김슬아 ( Seula Kim ),이영득 ( Young Deuk Lee ),정명근 ( Myo 한국환경농학회 2013 한국환경농학회 학술대회집 Vol.2013 No.-

Quintozene, pentachloronitrobenzene(PCNB) is a contact fungicide for control of soilborne phytopathogenic fungi during cultivation of diverse crops. It was introduced to agricultural use around 1930`s as a substitute for mercurial disinfectants. Although quintozene had been first registered in Korea in 1969 but now banned to use due to its high residue levels in selected harvests, high possibility is expected that the residue may be contained in imported agricultural commodities as it is still used widely over the world. Therefore, this study was conducted to establish a determination method for quintozene residue in crops using GC/ECD/MS. Quintozene residue was extracted with acetonitrile from representative samples of five raw products which comprised hulled rice, soybean, Chinese cabbage, green pepper, and apple. The extract was diluted with saline water, and n-hexane partition was followed to recover quintozene from the aqueous phase. Florisil column chromatography was additionally employed for final clean up of the extract. The quintozene was quantitated by GLC with ECD, using a DB-1 capillary column. The crops were fortified with quintozene at 3 levels per crop. Mean recoveries ranged from 79.9% to 102.7% in five representative agricultural commodities. The coefficients of variation were less than 4.3%. Quantitative limit of quintozene was 0.004 mg/kg in representative five crop samples. A GC/MS with selected-ion monitoring was also provided to confirm the suspected residue. Therefore, this analytical method was reproducible and sensitive enough to determine the residue of quintozene in agricultural commodities.

GC-ECD/MS를 이용한 농산물 중 Fipronil의 잔류 분석법 개발

안경근 ( Kyung Geun Ahn ),김경하 ( Gyeong Ha Kim ),김기쁨 ( Gi Ppeum Kim ),황영선 ( Young Sun Hwang ),강인규 ( In Kyu Kang ),이영득 ( Young Deuk Lee ),정명근 ( Myoung Gun Choung ) 한국환경농학회 2015 한국환경농학회지 Vol.34 No.4

BACKGROUND: An analytical method was developed using GC-ECD/MS to precisely determine the residue of fipronil, a phenylpyrazole insecticide used to control a wide range of foliar and soil-borne pests.METHOD AND RESULTS: Fipronil residue was extracted with acetone from representative samples of five raw products which comprised hulled rice, soybean, Kimchi cabbage, green pepper, and apple. The extract was diluted with saline water, and fipronil was partitioned into n-hexane/dichloromethane (20/80, v/v) to remove polar co-extractives in the aqueous phase. Florisil column chromatography was additionally employed for final purification of the extract. Fipronil was separated and quantitated by GC-ECD using a DB-17 capillary column.Accuracy of the proposed method was validated by the recovery from crop samples fortified with fipronil at 3 levels per crop in each triplication.CONCLUSION: Mean recoveries ranged from 86.6% to 106.0% in five representative agricultural commodities.The coefficients of variation were less than 10%. Limit of quantitation of fipronil was 0.004 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 residue. Therefore, this analytical method was reproducible and sensitive enough to determine the residue of fipronil in agricultural commodities.

GC-ECD/MS를 이용한 농산물 중 Quintozene의 잔류분석

안경근(Kyung-Geun Ahn),김경하(Gyeong-Ha Kim),김기쁨(Gi-Ppeum Kim),황영선(Young-Sun Hwang),홍승범(Seung-Beom Hong),이영득(Young Deuk Lee),정명근(Myoung-Gun Choung) 한국농약과학회 2015 농약과학회지 Vol.19 No.3

주요 농산물 중 Bezenesulfonamide계 살균제 Flusulfamide의 잔류 분석법

안경근 ( Kyung-geun Ahn ),김기쁨 ( Gi-ppeum Kim ),황영선 ( Young-sun Hwang ),강인규 ( In-kyu Kang ),이영득 ( Young Deuk Lee ),정명근 ( Myoung-gun Choung ) 한국환경농학회 2018 한국환경농학회지 Vol.37 No.1

본 연구에서는 HPLC-UVD/MS를 이용한 농산물 중benzenesulfonamide계 살균제 flusulfamide의 잔류 분석법을 확립하였다. 대표 농산물은 사과, 고추, 배추, 현미 및 콩을 적용하였고, acetone에 의해 추출된 flusulfamide 성분을 dichloromethane 액-액 분배법과 Florisil 흡착크로마토그래피법으로 정제하여 HPLC-UVD/MS의 분석시료로 사용하였다. Flusulfamide의 정량적 분석을 위한 최적HPLC-UVD 분석 조건을 검토하였으며, 정량한계(LOQ)는 0.02 mg/kg 이었다. 각 대표 농산물에 대해 정량한계, 정량 한계의 10배 및 50배 수준에서 회수율을 검토한 결과, 모든 처리농도에서 82.3-98.2% 수준의 회수율을 나타내었고, 반복간 변이계수(CV)는 최대 6.5%를 나타내어 잔류분석 기준인 회수율 70-120% 및 분석오차 10% 이내를 충족시키는 만족한 결과를 도출하였고, LC/MS/SIM을 이용하여 실제 농산물 시료에 적용하여 재확인 하였다. 이상의 결과로 신규flusulfamide의 HPLC-UVD/MS 분석법은 검출한계, 회수율 및 분석오차 면에서 국제적 분석기준을 만족하는 신뢰성이 확보된 정량 분석법으로 사용 가능할 것이다. BACKGROUND: An analytical method was developed using HPLC-UVD/MS to precisely determine the residue of flusulfamide, a benzenesulfonamide fungicide used to inhibit spore germination. METHODS AND RESULTS: Flusulfamide residue was extracted with acetone from representative samples of five raw products which comprised apple, green pepper, Kimchi cabbage, hulled rice, and soybean. The extract was diluted with large volume of saline water and directly partitioned into dichloromethane 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. On an octadecylsilyl column in HPLC, flusulfamide was successfully separated from co-extractives of sample, and sensitively quantitated by ultraviolet absorption at 280 nm with no interference. Accuracy and precision of the proposed method was validated by the recovery experiment on every crop sample fortified with flusulfamide at 3 concentration levels per crop in each triplication. CONCLUSION: Mean recoveries ranged from 82.3 to 98.2% 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 flusulfamide was 0.02 mg/kg as verified by the recovery experiment. A confirmatory method using LC/MS with selected-ion monitoring technique was also provided to clearly identify the suspected residue.

HPLC-UVD/MS를 이용한 농산물 중 Amisulbrom의 잔류분석

안경근(Kyung-Geun Ahn),김경하(Gyeong-Ha Kim),김기쁨(Gi-Ppeum Kim),김민지(Min-Ji Kim),황영선(Young-Sun Hwang),홍승범(Seung-Beom Hong),이영득(Young Deuk Lee),정명근(Myoung-Gun Choung) 한국농약과학회 2014 농약과학회지 Vol.18 No.4

엇갈이배추 재배기간 중 살균제 Amisulbrom의 생산단계 잔류허용기준 설정

안경근 ( Kyung Geun Ahn ),김경하 ( Gyeong Ha Kim ),김기쁨 ( Gi Ppeum Kim ),김민지 ( Min Ji Kim ),홍승범 ( Seung Beom Hong ),황영선 ( Young Sun Hwang ),권찬혁 ( Chan Hyeok Kwon ),손영욱 ( Young Wook Son ),이영득 ( Young Deuk Lee 한국환경농학회 2015 한국환경농학회지 Vol.34 No.2

BACKGROUND: Supervised residue trials were conducted to establish pre-harvest residue limit(PHRL), a criterion to ensure the safety of the pesticide residue in the crop harvest, of amisulbrom for winter-grown cabbage in two fields. Following to application of amisulbrom on the crop, time-course study was carried out to obtain the amisulbrom dissipation of statistical significance which enabled to calculate the predicted values of PHRL. METHOD AND RESULTS: During cultivation under greenhouse condition, samples of winter-grown cabbage were collected at 0, 1, 3, 5, 7 and 10 days after amisulbrom application, and subjected to residue analysis. Analytical method was validated by recoveries ranging 93.7~100.0% as well as limit of quantitation(LOQ) of 0.04 mg/kg. Amisulbrom residues in winter-grown cabbage gradually decreased as time elapsed. The dissipation rate of the residue would be affected by intrinsic degradation along with dilution by the cabbage growth. The decay pattern was well fitted by the simple first-order kinetics. CONCLUSION: Biological half-lives of amisulbrom in winter-grown cabbage ranged 3.7~4.1 days in two field conditions. Based on the regression of amisulbrom dissipation, PHRLs of amisulbrom in winter-grown cabbage were recommended as 8.86~9.47 and 4.21~4.35mg/kg for 10 and 5 days before harvest, respectively.

수출입 원예작물의 검역을 위한 살균제 Fluazinam의 공정 잔류분석법 개발

김경하(Gyeong-Ha Kim),안경근(Kyung-Geun Ahn),김기쁨(Gi-Ppeum Kim),황영선(Young-Sun Hwang),장문익(Moon-Ik Chang),강인규(In-Kyu Kang),이영득(Young Deuk Lee),정명근(Myoung-Gun Choung) 한국원예학회 2016 원예과학기술지 Vol.34 No.1

본 연구는 국내 및 수출입 원예작물의 일상적 잔류농약 검사에 활용 가능한 dinitroaniline계 광범위 살균제 fluazinam의 GC-ECD/MS 잔류 분석법을 확립하고자 하였다. 원예작물 중 채소류에서는 청양고추와 결구배추를, 과일류에서는 감귤과 사과를 대표 시료로 선정하였고, 아세톤으로 추출된 fluazinam은 식염수로 희석하고, 수용액층을 n-hexane 액-액 분배법으로 회수하였으며, 회수된 추출액으로부터 fluazinam의 최종적 정제를 위하여 florisil 칼럼 크로마토그래피법으로 추가 정제하여 GC-ECD/MS 분석용 시료로 사용하였다. Fluazinam의 정량적 분석을 위하여 DB-17 capillary column을 적용한 GC-ECD 분석 조건을 확립하였으며, 각 작물별 4수준의 농도로 fluazinam을 인위 첨가하여 회수율을 분석하였다. 각 대표 원예작물에 대해 정량한계, 정량한계의 10, 50, 및 100배 수준에서 회수율을 검토한 결과 모든 처리농도에서 82.5-99.9% 수준을 나타내었으며, 정량한계(LOQ)는 0.004mgㆍkg<SUP>-1</SUP>이었다. 반복 간 변이계수(CV)는 최대 6.6%를 나타내어 국제적 잔류분석 기준인 회수율 70-120% 및 분석오차 10% 이내를 충족시키는 만족한 결과를 도출하였다. 또한 GC/MS SIM을 이용하여 실제 각 작물 시료에 적용하여 재확인 하였다. 이상의 결과로 신규 fluazinam의 GC-ECD/MS 분석법은 검출한계, 회수율 및 분석오차 면에서 국제적 분석기준을 만족하는 신뢰성이 확보된 정량 분석법으로서 국내 및 수출입 검역을 위한 원예작물의 공정 잔류분석법으로 사용 가능할 것이다. This experiment was conducted to establish an official determination method to measure fluazinam residue in horticultural crops for import and export using GC-ECD/MS. Fluazinam residue was extracted with acetone from fresh samples of four representative horticultural products, the vegetable crops green pepper and kimchi cabbage, and the fruit crops mandarin and apple. The acetone extract was diluted with saline water and n -hexane partitioning was used to recover fluazinam from the aqueous phase. Florisil column chromatography was additionally employed for final purification of the extract. Fluazinam was separated and quantitated by GC with ECD using a DB-17 capillary column. The horticultural crops were fortified with three different concentrations of fluazinam. Mean recoveries ranged from 82.5% to 99.9% in the four crops. The coefficients of variation were less than 10.0%. The quantitative limit of fluazinam detection was 0.004 mgㆍkg<SUP>-1</SUP> in the four crop samples. GC/MS with selected-ion monitoring was also used to confirm the suspected residue. This analytical method was reproducible and sensitive enough to measure the residue of fluazinam in horticultural commodities for import and export.

채소류의 수확 후 원재료 및 데침 처리에 의한 비타민 B<SUB>5</SUB> 및 B<SUB>6</SUB> 함량 변화

김기쁨(Gi-Ppeum Kim),안경근(Kyung-Geun Ahn),김경하(Gyeong-Ha Kim),황영선(Young-Sun Hwang),강인규(In-Kyu Kang),최용민(Youngmin Choi),김행란(Haeng-Ran Kim),정명근(Myoung-Gun Choung) 한국원예학회 2016 원예과학기술지 Vol.34 No.1

국내 다소비 채소류 39종에 대해 원재료 및 데침 조리 시 함유된 수용성 비타민 B5 및 B6의 함량변화를 자외부 흡광 검출기(HPLC/DAD) 및 형광검출기(HPLC/FLD)로 분리 검출하였다. 각 성분의 분석법을 밸리데이션하여 신뢰도 높은 분석법임을 확인한 후 조제분유를 이용하여 내부 분석품질을 관리하였고, 비타민 B6의 경우에는 국제 정도 관리를 통하여 정밀한 분석 수행능력을 평가 받았다. 검증된 분석법으로 채소류 39종의 원재료 및 데침 조리 시 비타민 B5 및 B6 함량 변화를 분석한 결과, 비타민 B5의 경우 근채류에서는 마늘, 엽채류에서는 포항초, 경채류는 두릅, 과채류의 숙과용 호박이 각각의 분류에서 가장 높은 함량을 나타내었으며, 그 중 경채류인 두릅(2.462mg·100g<SUP>-1</SUP>)이 가장 높은 함량을 나타내었다. 비타민 B6의 경우에는 근채류에서 마늘, 엽채류에서는 근대, 경채류는 마늘쫑, 과채류의 적색토마토가 각각의 분류에서 가장 높은 함량을 나타내었고, 그 중 엽채류의 근대(0.127mg·100g<SUP>-1</SUP>)가 가장 높은 함량으로 평가되었다. 대부분의 채소류에서 데침 처리 시 원재료에 비해 B5 및 B6의 함량이 감소하거나 검출되지 않는 양상을 나타내었으며, 특히 비타민 B5는 두릅, 비타민 B6는 노란감자 및 근대에서 각각 약 20배 및 4배 대폭 감소하는 경향을 나타내었다. 이 결과는 채소작물의 이용 및 가공, 국민 식생활 정보 및 학교 조리 급식 등 영양적 부분과 국민 건강을 위한 중요한 기초자료로 이용될 수 있을 것이다. This study was aimed to determine the changes in vitamin B5 and B6 contents compared to fresh materials after parboiling treatment of the main vegetables consumed in Korea. The specificity of accuracy and precision for vitamin B5 and B6 analysis method were validated using highperformance liquid chromatography (HPLC). The recovery rate of standard reference material (SRM) was excellent, and all analysis was under the control line based on the quality control chart for vitamin B5 and B6. The Z-score for vitamin B6 in food analysis performance assessment scheme (FAPAS) proficiency test was -1.0, confirming reliability of analytical performance. The vitamin B5 and B6 contents in a total of 39 fresh materials and parboiled samples were analyzed. The contents of vitamin B5 and B6 ranged from 0.000 to 2.462 and from 0.000 to 0.127 mg · 100g<SUP>-1</SUP>, respectively. The highest contents of vitamin B5 and B6 were 2.462 mg · 100g<SUP>-1</SUP> in fresh fatsia shoots (stem vegetables), and 0.127 mg · 100g<SUP>-1</SUP> in fresh spinach beet (leafy vegetables), respectively. Moreover, the vitamin B5 and B6 contents for parboiling treatment in most vegetables were reduced or not detected. In particular, the contents of vitamin B5 in parboiled fatsia shoots and vitamin B6 in parboiled yellow potato and spinach beet were decreased 20- and 4-fold compared with fresh material, respectively. These results can be used as important basic data for utilization and processing of various vegetable crops, information for dietary life, management of school meals, and national health for Koreans.