본 연구는 과수, 엽채류 등과 같은 식품 내에 잔류하는 살균제 dithiocarbamate계의 분석법 개선에 관한 것이다. 세계 각 국에서 보편적으로 사용되고 있으나, dithiocarbamate계 농약의 성분별 정성 및 정량이 불가능하고, 분석에 많은 시간이 소요되는 CS2 법의 한계와 용해성과 회수율에 문제가 있는 종래의 HPLC 법의 문제점 등을 개선하고자 신속하고 정확한 최적의 HPLC 법을 연구하였다. 또한 개선된 HPLC법의 효율성은 LC/MS/MS에 의해 검증되어졌다. Dithiocarbamate계 농약의 HPLC 분석방법 개선을 통해 얻어진 분석방법의 적용실험은 dithiocarbamate계 농약 중 사용량이 많을 뿐만 아니라 발암가능성이 있어 생산량을 규제하고 있는 mancozeb 농약을 국립농산물품질관리원 각 지원에서 살포하여 채취한 농산물 중 상추, 고추, 오이 깻잎, 방울토마토, 포도 총 70점을 제공받아 개선된 HPLC법과 세계적으로 사용되고 있는 CS2 분석법을 비교 실험하였으며, 또한 mancozeb 농약을 농산물 중 고추, 방울토마토 등 10개 품목을 선정하여 각각 엽면 살포 후 세척방법에 따른 작물별 ...
본 연구는 과수, 엽채류 등과 같은 식품 내에 잔류하는 살균제 dithiocarbamate계의 분석법 개선에 관한 것이다. 세계 각 국에서 보편적으로 사용되고 있으나, dithiocarbamate계 농약의 성분별 정성 및 정량이 불가능하고, 분석에 많은 시간이 소요되는 CS2 법의 한계와 용해성과 회수율에 문제가 있는 종래의 HPLC 법의 문제점 등을 개선하고자 신속하고 정확한 최적의 HPLC 법을 연구하였다. 또한 개선된 HPLC법의 효율성은 LC/MS/MS에 의해 검증되어졌다. Dithiocarbamate계 농약의 HPLC 분석방법 개선을 통해 얻어진 분석방법의 적용실험은 dithiocarbamate계 농약 중 사용량이 많을 뿐만 아니라 발암가능성이 있어 생산량을 규제하고 있는 mancozeb 농약을 국립농산물품질관리원 각 지원에서 살포하여 채취한 농산물 중 상추, 고추, 오이 깻잎, 방울토마토, 포도 총 70점을 제공받아 개선된 HPLC법과 세계적으로 사용되고 있는 CS2 분석법을 비교 실험하였으며, 또한 mancozeb 농약을 농산물 중 고추, 방울토마토 등 10개 품목을 선정하여 각각 엽면 살포 후 세척방법에 따른 작물별 잔류농약 세척효과를 알아보았다. 개선된 HPLC분석법의 타당성을 검증해 본 결과 DDC(thiram, ziram, ferbam)의 검출한계는 0.005mg/L, 정량한계는 0.002mg/L, 검량선식은 Y=236.05X-35.0951로 r2값은 0.9997이었고, EBDC(maneb, zineb, mancozeb, metiram, nabam)의 검출한계는 0.005mg/L, 정량한계는 0.001mg/L, 검량선식은 Y=426.4397X-0.9957로 r2값은 1.0000이었으며, PBDC(propineb)의 검출한계는 0.05mg/L, 정량한계는 0.1mg/L, 검량선식은 Y=18.753X-1.8822로 r2값은 0.9999이었다. 농약표준용액 검량선의 재현성도 7일 동안의 검사결과 DDC는 r2값이 0.9968～0.9997, EBDC는 r2값이 0.9997～1.0000, PBDC는 r2값이 0.9995～0.9999로 직선성이 우수하였고, 분석결과의 재현성은 6회 연속으로 반복 측정한 결과 변이계수 값이 DDC는 0.31％, EBDC는 0.78％ , PBDC는 0.73％로 2％내의 낮은 변이율을 나타내어 본 분석조건에서 기기 안정성이 우수하여 분석의 신뢰성을 입증하였다. 농산물 중에 처리한 각 농약의 회수율을 측정한 결과 평균회수율은 DDC의 경우 88.36～104.13％, EBDC는 97.98～103.35％ , PBDC는 97.40～98.34％이었으며, 변이계수(CV)는 DDC는 7.43％, EBDC는 2.78％ , PBDC는 0.52％로 분석 간의 편차가 크지 않았다. LC/MS/MS를 이용하여 개선된 HPLC법의 효율성을 검증해 본 결과 DDC의 검출한계는 0.01mg/L, 정량한계는 0.02mg/L, 검량선 식은 Y=3.5568X+4.093으로 r2값은 0.9983이었고, EBDC의 검출한계는 0.001mg/L, 정량한계는 0.001mg/L, 검량선 식은 Y=2.9307X -0.8197로 r2값은 0.9994이었으며, PBDC의 검출한계는 0.001mg/L, 정량한계는 0.001mg/L, 검량선 식은 Y=3.0125X-4.2439로 r2값은 0.9978이었다 분석결과의 재현성은 6회 연속으로 반복 측정한 결과 변이계수 값이 DDC는 0.14％, EBDC는 0.20％, PBDC는 0.19％로 2％내의 낮은 변이율을 나타내어 본 분석조건에서 기기안정성이 우수하여 분석의 신뢰성을 입증하였다. 개선된 분석법 적용을 위해 HPLC법과 CS2 분석법을 비교 실험한 결과, HPLC법의 경우 검출한계, 품목별 회수율 및 변이계수는 0.005mg/L, 87.37~100.23％, 2.78~5.36％이었고, CS2법은 0.5mg/L, 85.21~93.30％, 1.64~6.71％이었다. 분석 소요시간은 HPLC법의 경우 3시간, CS2법은 16시간이 소요되어 큰 차이를 보였다. 고추, 방울토마토 등 10개 품목을 선정하여 작물별 잔류농약 세척효과를 알아본 결과, 품목별 처음농도는 1.05~12.02이었고, 세척 후 농도는 수돗물에서 N.D~0.79, 양조식초에서 N.D~0.41, 현미식초에서 N.D~0.53, 과일 야채용 세제 추천량(1％)세제에서 N.D~0.07로 세척효율은 89.60~100％를 나타내었으며, 모든 품목이 MRL 기준이하로 안전하였다.
본 연구는 과수, 엽채류 등과 같은 식품 내에 잔류하는 살균제 dithiocarbamate계의 분석법 개선에 관한 것이다. 세계 각 국에서 보편적으로 사용되고 있으나, dithiocarbamate계 농약의 성분별 정성 및 정량이 불가능하고, 분석에 많은 시간이 소요되는 CS2 법의 한계와 용해성과 회수율에 문제가 있는 종래의 HPLC 법의 문제점 등을 개선하고자 신속하고 정확한 최적의 HPLC 법을 연구하였다. 또한 개선된 HPLC법의 효율성은 LC/MS/MS에 의해 검증되어졌다. Dithiocarbamate계 농약의 HPLC 분석방법 개선을 통해 얻어진 분석방법의 적용실험은 dithiocarbamate계 농약 중 사용량이 많을 뿐만 아니라 발암가능성이 있어 생산량을 규제하고 있는 mancozeb 농약을 국립농산물품질관리원 각 지원에서 살포하여 채취한 농산물 중 상추, 고추, 오이 깻잎, 방울토마토, 포도 총 70점을 제공받아 개선된 HPLC법과 세계적으로 사용되고 있는 CS2 분석법을 비교 실험하였으며, 또한 mancozeb 농약을 농산물 중 고추, 방울토마토 등 10개 품목을 선정하여 각각 엽면 살포 후 세척방법에 따른 작물별 잔류농약 세척효과를 알아보았다. 개선된 HPLC분석법의 타당성을 검증해 본 결과 DDC(thiram, ziram, ferbam)의 검출한계는 0.005mg/L, 정량한계는 0.002mg/L, 검량선식은 Y=236.05X-35.0951로 r2값은 0.9997이었고, EBDC(maneb, zineb, mancozeb, metiram, nabam)의 검출한계는 0.005mg/L, 정량한계는 0.001mg/L, 검량선식은 Y=426.4397X-0.9957로 r2값은 1.0000이었으며, PBDC(propineb)의 검출한계는 0.05mg/L, 정량한계는 0.1mg/L, 검량선식은 Y=18.753X-1.8822로 r2값은 0.9999이었다. 농약표준용액 검량선의 재현성도 7일 동안의 검사결과 DDC는 r2값이 0.9968～0.9997, EBDC는 r2값이 0.9997～1.0000, PBDC는 r2값이 0.9995～0.9999로 직선성이 우수하였고, 분석결과의 재현성은 6회 연속으로 반복 측정한 결과 변이계수 값이 DDC는 0.31％, EBDC는 0.78％ , PBDC는 0.73％로 2％내의 낮은 변이율을 나타내어 본 분석조건에서 기기 안정성이 우수하여 분석의 신뢰성을 입증하였다. 농산물 중에 처리한 각 농약의 회수율을 측정한 결과 평균회수율은 DDC의 경우 88.36～104.13％, EBDC는 97.98～103.35％ , PBDC는 97.40～98.34％이었으며, 변이계수(CV)는 DDC는 7.43％, EBDC는 2.78％ , PBDC는 0.52％로 분석 간의 편차가 크지 않았다. LC/MS/MS를 이용하여 개선된 HPLC법의 효율성을 검증해 본 결과 DDC의 검출한계는 0.01mg/L, 정량한계는 0.02mg/L, 검량선 식은 Y=3.5568X+4.093으로 r2값은 0.9983이었고, EBDC의 검출한계는 0.001mg/L, 정량한계는 0.001mg/L, 검량선 식은 Y=2.9307X -0.8197로 r2값은 0.9994이었으며, PBDC의 검출한계는 0.001mg/L, 정량한계는 0.001mg/L, 검량선 식은 Y=3.0125X-4.2439로 r2값은 0.9978이었다 분석결과의 재현성은 6회 연속으로 반복 측정한 결과 변이계수 값이 DDC는 0.14％, EBDC는 0.20％, PBDC는 0.19％로 2％내의 낮은 변이율을 나타내어 본 분석조건에서 기기안정성이 우수하여 분석의 신뢰성을 입증하였다. 개선된 분석법 적용을 위해 HPLC법과 CS2 분석법을 비교 실험한 결과, HPLC법의 경우 검출한계, 품목별 회수율 및 변이계수는 0.005mg/L, 87.37~100.23％, 2.78~5.36％이었고, CS2법은 0.5mg/L, 85.21~93.30％, 1.64~6.71％이었다. 분석 소요시간은 HPLC법의 경우 3시간, CS2법은 16시간이 소요되어 큰 차이를 보였다. 고추, 방울토마토 등 10개 품목을 선정하여 작물별 잔류농약 세척효과를 알아본 결과, 품목별 처음농도는 1.05~12.02이었고, 세척 후 농도는 수돗물에서 N.D~0.79, 양조식초에서 N.D~0.41, 현미식초에서 N.D~0.53, 과일 야채용 세제 추천량(1％)세제에서 N.D~0.07로 세척효율은 89.60~100％를 나타내었으며, 모든 품목이 MRL 기준이하로 안전하였다.
The present study was conducted on the development of analysis method the residual fungicides of the dithiocarbamate group in the fruits and vegetables. The present CS2 analysis method takes long time to analyze and present HPLC analysis has solubility problem of the fungicides and low recovery rate...
The present study was conducted on the development of analysis method the residual fungicides of the dithiocarbamate group in the fruits and vegetables. The present CS2 analysis method takes long time to analyze and present HPLC analysis has solubility problem of the fungicides and low recovery rates. The objectives of present study was to solve these problems by making the derivative of dithiocarbamate fungicides and detecting this derivatives by HPLC. This improved method was confirmed with LC/MS/MS analysis. This new improved HPLC method was applied to detect the fungicide, widely used macozeb of dithiocarbamate group from 70 samples of lettuce, cherry tomato, cucumber, perilla leaf, pepper, and grape which had been treated with that fungicide. The results with new improved method were compared with CS2. Finally the effect of washing methods on removal of the residual fungicide of mancozeb was studied after the fungicide was applied to 10 items including pepper, cherry tomato, lettuce, perilla leaf, and spinach. The new analysis of HPLC detected the DDC (thiram, febram and ziram) at limit of 0.005mg/L and the quantitative limit was 0.002mg/L. The standard curve for this was Y=236.05X-35.0951 and r2 was equal to 0.9997. The detection limit of EBDC (maneb, mancozeb, metiram, zineb and nabam) was 0.005mg/L and the quantitative limit was 0.001mg/L. The standard curve for this was Y=426.4397X-0.9957 and r2 was equal to 1.0000. The detection limit of PBDC (propineb) was 0.05mg/L and the quantitative limit was 0.1mg/L. The standard curve for this was Y=18.753X-1.8822 and r2 was equal to 0.9999. Reproducibility of detection of fungicides was very high as coefficiency of variation of 6 consecutive experiments was 0.31% for DDC, 0.78% for EBDC, 0.73% for PBDC. Also there was strong linearity of the standard curves as r2 for DDC was 0.9968～0.9997, r2 of EBDC was 0.9997～1.0000 and r2 of PBDC was 0.9995～0.9999. The mean recovery rates from the crops treated with the respective pesticides were 88.36～104.13％ for DDC, 97.98～103.35％for EBDC, and 97.40～98.34％ for PBDC. The coefficiency of variations were 7.43％ for DDC, 2.78％ for EBDC and 0.52％ for PBDC. As the results of LC/MS/MS analysis for dithiocarbamate, the detection limit of DDC was 0.01mg/L and the quantitative limit was 0.02mg/L. The standard curve for this was Y=3.5568X+4.093 and r2 was equal to 0.9983. The detection limit of EBDC was 0.001mg/L and the quantitative limit was 0.001mg/L. The standard curve for this was Y=2.9307X-0.8197 and r2 was equal to 0.9994. The detection limit of PBDC was 0.001mg/L and the quantitative limit was 0.001mg/L. The standard curve for this was Y=3.0125X-4.2439 and r2 was equal to 0.9978. Reproducibility of detection of fungicides was very high as coefficiency of variation of 6 consecutive experiments was 0.14% for DDC, 0.20% for EBDC, 0.19% for PBDC. In terms of recovery rates by new HPLC and CS2 methods for the comparison purpose, the recovery rates of the new HPLC was ranged in 87.37~100.23％, depending on the fruit and vegetable samples. In contrast, those of the CS2 method was ranged in 85.21~93.30％. Coefficiency of variation for HPLC and CS2 method was 2.78~5.36％ and 1.64~6.71％, respectively. The detection limits of HPLC as 0.005mg/L was much superior to CS2 method as 0.5mg/L. In addition, required time for analysis of 10 samples by new HPLC was 3 hrs. However that for CS2 method was 16 hrs. Residual concentration of 10 vegetables including peppers and cherry tomatoes was in ranges from not detectable (N.D.) to 0.79mg/L through washing with tap water, N.D. to 0.41mg/L through washing with manufacture vinegar, N.D. to 0.53mg/L through washing with rice vinegar, N.D. to 0.07mg/L (89.60~100% removal rate) through washing with 1% detergent from initial residual concentration of 1.05~12.02 mg/L. All the samples washed with the above methods showed the safe level below MRL standard.
The present study was conducted on the development of analysis method the residual fungicides of the dithiocarbamate group in the fruits and vegetables. The present CS2 analysis method takes long time to analyze and present HPLC analysis has solubility problem of the fungicides and low recovery rates. The objectives of present study was to solve these problems by making the derivative of dithiocarbamate fungicides and detecting this derivatives by HPLC. This improved method was confirmed with LC/MS/MS analysis. This new improved HPLC method was applied to detect the fungicide, widely used macozeb of dithiocarbamate group from 70 samples of lettuce, cherry tomato, cucumber, perilla leaf, pepper, and grape which had been treated with that fungicide. The results with new improved method were compared with CS2. Finally the effect of washing methods on removal of the residual fungicide of mancozeb was studied after the fungicide was applied to 10 items including pepper, cherry tomato, lettuce, perilla leaf, and spinach. The new analysis of HPLC detected the DDC (thiram, febram and ziram) at limit of 0.005mg/L and the quantitative limit was 0.002mg/L. The standard curve for this was Y=236.05X-35.0951 and r2 was equal to 0.9997. The detection limit of EBDC (maneb, mancozeb, metiram, zineb and nabam) was 0.005mg/L and the quantitative limit was 0.001mg/L. The standard curve for this was Y=426.4397X-0.9957 and r2 was equal to 1.0000. The detection limit of PBDC (propineb) was 0.05mg/L and the quantitative limit was 0.1mg/L. The standard curve for this was Y=18.753X-1.8822 and r2 was equal to 0.9999. Reproducibility of detection of fungicides was very high as coefficiency of variation of 6 consecutive experiments was 0.31% for DDC, 0.78% for EBDC, 0.73% for PBDC. Also there was strong linearity of the standard curves as r2 for DDC was 0.9968～0.9997, r2 of EBDC was 0.9997～1.0000 and r2 of PBDC was 0.9995～0.9999. The mean recovery rates from the crops treated with the respective pesticides were 88.36～104.13％ for DDC, 97.98～103.35％for EBDC, and 97.40～98.34％ for PBDC. The coefficiency of variations were 7.43％ for DDC, 2.78％ for EBDC and 0.52％ for PBDC. As the results of LC/MS/MS analysis for dithiocarbamate, the detection limit of DDC was 0.01mg/L and the quantitative limit was 0.02mg/L. The standard curve for this was Y=3.5568X+4.093 and r2 was equal to 0.9983. The detection limit of EBDC was 0.001mg/L and the quantitative limit was 0.001mg/L. The standard curve for this was Y=2.9307X-0.8197 and r2 was equal to 0.9994. The detection limit of PBDC was 0.001mg/L and the quantitative limit was 0.001mg/L. The standard curve for this was Y=3.0125X-4.2439 and r2 was equal to 0.9978. Reproducibility of detection of fungicides was very high as coefficiency of variation of 6 consecutive experiments was 0.14% for DDC, 0.20% for EBDC, 0.19% for PBDC. In terms of recovery rates by new HPLC and CS2 methods for the comparison purpose, the recovery rates of the new HPLC was ranged in 87.37~100.23％, depending on the fruit and vegetable samples. In contrast, those of the CS2 method was ranged in 85.21~93.30％. Coefficiency of variation for HPLC and CS2 method was 2.78~5.36％ and 1.64~6.71％, respectively. The detection limits of HPLC as 0.005mg/L was much superior to CS2 method as 0.5mg/L. In addition, required time for analysis of 10 samples by new HPLC was 3 hrs. However that for CS2 method was 16 hrs. Residual concentration of 10 vegetables including peppers and cherry tomatoes was in ranges from not detectable (N.D.) to 0.79mg/L through washing with tap water, N.D. to 0.41mg/L through washing with manufacture vinegar, N.D. to 0.53mg/L through washing with rice vinegar, N.D. to 0.07mg/L (89.60~100% removal rate) through washing with 1% detergent from initial residual concentration of 1.05~12.02 mg/L. All the samples washed with the above methods showed the safe level below MRL standard.
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