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1 Korean Journal of Environmental Agriculture Korean J Environ Agric. 2015;34(2): Korean Online ISSN: Published online 2015 June Print ISSN: Research Article Open Access 엇갈이배추재배기간중살균제 Amisulbrom 의생산단계잔류허용기준설정 안경근 1, 김경하 1, 김기쁨 1, 김민지 1, 홍승범 1, 황영선 1,2, 권찬혁 3, 손영욱 3, 이영득 4, 정명근 1* 1 강원대학교생약자원개발학과, 2 텍사스주립대학교생물학과, 3 식품의약품안전처식품기준과, 4 대구대학교생명환경학부 Establishment of Pre-Harvest Residue Limit(PHRL) of the Fungicide Amisulbrom during Cultivation of Winter-Grown Cabbage Kyung-Geun Ahn 1, Gyeong-Ha Kim 1, Gi-Ppeum Kim 1, Min-Ji Kim 1, Seung-Beom Hong 1, Young-Sun Hwang 1,2, Chan-Hyeok Kwon 3, Young Wook Son 3, Young Deuk Lee 4 and Myoung-Gun Choung 1 * ( 1 Department of Herbal Medicine Resource, Kangwon National University, Samcheok, , Korea, 2 Department of Biology, University of Texas-Arlington, Arlington, TX 76019, USA, 3 Food Standard Division, Ministry of Food and Drug Safety, Cheongju, , Korea, 4 Division of Life and Environmental Science, Daegu University, Gyeongsan, , Korea) Received: 2 December 2014 / Revised: 27 May 2015 / Accepted: 22 June 2015 Copyright c 2015 The Korean Society of Environmental Agriculture This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License ( which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited. Abstract 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 % 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 *Corresponding author: Myoung-Gun Choung Phone: ; Fax: ; cmg7004@kangwon.ac.kr 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 days in two field conditions. Based on the regression of amisulbrom dissipation, PHRLs of amisulbrom in winter-grown cabbage were recommended as and mg/kg for 10 and 5 days before harvest, respectively. Key words: Amisulbrom, Biological half-life, Pre-harvest residue limit(phrl), Winter-grown cabbage 서론 농약은현대농업에서필수불가결한존재로써생산량증가, 품질향상및노동력절감에큰공헌을하고있다. 그러나농약은생물의생리작용을저해하는작용을나타내므로근본적으로독성을가지며, 작물에살포된후농약의특성이나환경조건에따라그정도는상이하나필연적으로수확물에잔류하게된다. 따라서농약이잔류하는농작물혹은식품을섭 120

2 Establishment of PHRL of Amisulbrom on Winter-Grown Cabbage 121 Table 1. Physicochemical properties of amisulbrom(macbean, 2012) Common name IUPAC name Amisulbrom 3-(3-bromo-6-fluoro-2-methylindol-1-ylsulfonyl)-N,N-dimethyl-1H-1,2,4- trazole-1-sulfonamide Molecular weight : Molecular formular : C 13H 13BrFN 5O 4S 2 Physical chemistry Melting point : Log P ow : 4.4 Water solubility : 0.11 mg/l(20 ) Vapor pressure : mpa(25 ) Chemical structure 취할경우건강에대한위해요인으로작용할가능성이상존하므로, 국제적수준에서는물론국가차원에서도농산물의농약잔류허용기준 (Maximum Residue Limit; MRL) 을설정하여관리, 감독하고있다 (Lee et al., 2008). 농약잔류허용기준 (MRL) 은수확후출하되는농산물및식품에잔류가허용되는최대농약잔류농도로정의되는데, 국내에서는 2014년 12월기준 440종의농약에대해농산물의농약잔류허용기준이설정되어있으며, 특히엇갈이배추에서는건조된것을포함하여 99종의농약에대해잔류허용기준이설정되어있다 (Ministry of Food and Drug Safety, 2014). 농산물의농약잔류검사는주로수확후또는유통단계에서이뤄지는데, MRL을초과한부적합농산물에대해서는대부분폐기처분되며, 이런조치는농산물생산, 유통및처리비용을부담하는생산자인농민에게막대한손실을초래하게된다. 일부농산물은수확물의유통기간이매우짧으므로출하후농약잔류검사제도로는분석결과가산출되는시점에이미유통이종료되어시기상관리및제재조치를하기가어렵다. 잔류농약검사가진행되는동안이미출하된농산물이소비자에게유통될경우건강상의문제를야기할수있기때문에농식품중잔류농약조사는국민보건상매우중요한사안이다 (Ko et al., 2003; Lee et al., 2008). 따라서농작물의잔류농약에대한안전성평가는출하전에이루어지는것이바람직할것이며 (Kim et al., 2002), 이러한문제점을해결하는가장적절한방법은생산기간중에살포된농약의잔류량을수확전일정기간동안조사하여합리적인잔류감소예측식을만들고, 이것에맞추어생산단계별잔류허용기준을설정하여관리하는것이바람직할것이다. 즉, 수확시잔류량을예측하여 MRL을초과할가능성이있는농산물을판별해출하연기또는폐기처분등의조치를조기에취할수있는것이다 (Choi et al., 2002; Ko et al., 2003; Seong et al., 2004; Lee et al., 2008; Kim et al., 2009). 이러한생산단계농약잔류허용기준 ; Pre-Harvest Residue Limit(PHRL) 을설정함에있어작물에살포된농약은환경조건및미생물에의한분해등여러요인과작물의증체에따른희석효과에의해그농도의변화정도가상이하 므로 (Hill and Inaba, 1990; Bentson, 1990), 재배기간중발생될수있는요인들을종합평가할수있는실제포장시험을수행하여농산물중잔류농약의감소율을평가하여야한다. 본연구의대상성분인 amisulbrom[3-(3-bromo-6-fluoro- 2-methylindol-1-ylsulfonyl)-N,N-dime-thyl-1H-1,2,4-tra zole-1-sulfonamide] 은세계적으로 2007년에최초로등록된 sulfonamide계살균제로병원균체내미토콘드리아의호흡을억제함으로써난균강에선택적으로작용하는약제로알려져있다 (MacBean, 2012). 외국에서는포도및감자의재배 (US/EPA, 2011), 국내에서는고추, 배추, 감자, 양파, 파, 수박, 토마토, 참깨등다양한작물의재배시에노균병, 뿌리혹병, 역병및뿌리썩음병을방제하는데사용되고있으며 (Korea Crop Protection Association, 2014), 엇갈이배추에대한 MRL은 2.0 mg/kg으로설정되어있다 (Ministry of Food and Drug Safety, 2014). 안전사용기준은배추의노균병방제에 10일간격으로살포하고, 수확 7일전까지 4회이내로살포하도록등록되어있다 (Korea Crop Protection Association, 2014). 따라서본연구에서는살균제 amisulbrom을엇갈이배추시설재배포장에살포하고일정기간별로수확, 엇갈이배추중의잔류수준을조사함과동시에통계학적유의성이인정되는분해감소회귀식과생물학적반감기를산출해엇갈이배추에대한 amisulbrom의수확전생산단계농약잔류허용기준을실증적으로설정코자하였다. 재료및방법 시약및기구본연구에사용한 amisulbrom은순도 99% 이상의분석용표준품을 Dr. Ehrenstorfer GmbH(Germany) 로부터구입하여사용하였다 (Table 1). 표준품의 stock solution은 acetonitrile에녹여 1000 mg/l의농도로조제하여 -20 의냉동고에서보관하고, 필요시마다 acetonitrile로희석하여사용하였다. Florisil( mesh) 은 J. T. Baker (USA) 로부터구입하여 130 에서하룻밤이상가열, 활성화

3 122 Ahn et al. Table 2. Formulation and safe use standard (Korea Crop Protection Association, 2009) Safe use standard Pesticide Formulation type A.I. 1) contents(%) Dilution (ml in 20 L water) PHI 2) (day) MAF 3) (time) Amisulbrom SC 4) Abbreviations : 1) Active ingredient, 2) Pre-harvest interval, 3) Maximum application frequency, 4) Suspension concentrate. Table 3. HPLC operating parameters for the analysis of amisulbrom HPLC system Agilent 1200 HPLC system Detector Agilent 1200 photodiode array UV detector Column YMC-Pack Pro C 18 RS( mm, 5 μm ) Column temp. 40 Mobile phase Water/acetonitrile(20/80, v/v) Flow rate 1.0 ml/min Wavelength UV 255 nm Injection vol. 20 μl 하여사용하였다. n-hexane, dichloromethane, acetonitrile 및 ethyl acetate는잔류분석용을, deionized water는 HPLC용을 J. T. Baker(USA) 에서구입하여사용하였다. 기타유기용매및무기시약은시약특급또는잔류분석용을사용하였다. 농축기는 Eyela NE-1000SW(Japan) 를사용하였고, 엇갈이배추시료의마쇄및균질화는고속호모게나이저 (IKA, Ultra-Turrax T-25, USA) 를이용하였다. 살포농약인 amisulbrom 13.5% 액상수화제 ( 상표명 : 명작 ) 는강원도삼척시소재농약시판상에서구입하였다 (Table 2). 공시작물및농약살포공시작물인엇갈이배추는한농종묘의 황금솎음 품종을공시하여경상북도칠곡군왜관읍 ( 포장 1) 과지천면 ( 포장 2) 에위치한시설재배농가에서재배하였다. 총시험면적 m 2 ( 포장 1) 및 78.2 m 2 ( 포장 2) 의시험포장에시험구를각각 3반복배치하고, 반복간완충대를 1 m 이상설치하여교차오염을방지하고자하였다. 공시약제인 amisulbrom 액상수화제 (13.5%) 를안전사용기준의최고기준량으로조제한후전동분무기를이용하여 ( 살포압력 3.0 kg/cm 2 ) 살포액이엇갈이배추에충분히흐를정도로 1회살포하였다. 농약살포후 2시간 (0일차), 1, 3, 5, 7 및 10일차에배추시료를각 1 kg 이상씩채취하여각각의무게를측정하고생장곡선을산출함과동시에잔류분석에공시하였다. 시설재배시각포장의온도와습도는 LASCAR (UK) 사의온습도 data logger(el-usb-2-lcd) 를이용하여측정하였다. HPLC/UVD 분석조건엇갈이배추중 amisulbrom의잔류분석에는자외흡광검출기 (UVD) 가장착된 Agilent(USA) 1200 series HPLC를사용하였다 (Table 3). 표준검량선및분석정량한계 Amisulbrom 의 stock solution을희석하여 mg/l의농도가되도록농도별표준용액을조제하고, 각 20 μl씩 HPLC에주입하여나타난 peak의면적을기준으로표준검량선을작성하였다. 분석법의정량한계는엇갈이배추대조구시료에서간섭물질이존재하지않음을확인한후, 분석기기의정량한계와시료량및분석과정중의농축배율을계산하여아래의계산식에의해산출하였으며 (Lee et al., 2011), 동일수준으로 amisulbrom을처리한회수율시험으로재확인하였다. LOQ(mg/kg)=[ 기기정량한계 (ng)/ 주입량 (μl)] [ 시료용액 (ml)/ 시료량 (g)] 분석기기의재현성 (Reproducibility) 검증 Amisulbrom 표준용액 (0.5 mg/l) 을 HPLC에 15번주입하여크로마토그램상의 retention time 및 peak area의변이를비교검토하여분석기기의재현성을평가하였다. 엇갈이배추중 amisulbrom 잔류분석시료의추출및정제엇갈이배추시료 25 g에 acetonitrile 100 ml를가하고호모게나이저상에서 2분간고속마쇄 (12,000 rpm) 추출하였다. 추출물을여과지 (Toyo No. 6, Japan) 가장착된 Buchner funnel 상에서여과하고시료및호모게나이저컵을여분의 acetonitrile 50 ml로씻어앞서의여과액과합하였다. 합친추출액을 1 L 용량의분액여두에옮기고포화식염수 50 ml 와증류수 450 ml를첨가한뒤 dichloromethane 50 ml 로 2회분배추출하였다. 합친 dichloromethane 추출액을무수 sodium sulfate에통과시켜탈수한후 40 에서감압농축, 건고하였다. 시료의잔류물은 n-hexane 10 ml에재용해하였다. 한편, 내경 1.5 cm, 길이 40 cm의유리컬럼에활

4 Establishment of PHRL of Amisulbrom on Winter-Grown Cabbage 123 성화시킨 Florisil 10 g을건식충전한후, 3 g의무수 sodium sulfate를그위에첨가하였다. 컬럼에 n-hexane 50 ml를가하여상단에소량의 n-hexane이남을정도로유출시켜버린후 n-hexane 10 ml에녹인시료용액을가하여약 3 ml/min의유속으로유출시켰다. 충진제표면이노출되기직전 n-hexane/ethyl acetate 혼합용액 (95/5, v/v) 100 ml를용출시켜버린후재차 n-hexane/ethyl acetate 혼합용액 (85/15, v/v) 150 ml를용출시켜받았다. Amisulbrom이용출된분획은 40 에서감압농축, 건고하고잔류물을 water/acetonitrile (20/80, v/v) 10 ml에재용해하여 HPLC로분석하였다. 회수율시험무처리엇갈이배추에 amisulbrom 표준용액을각각 0.4 및 2.0 mg/kg이되도록 3반복으로처리, 혼화한후상기분석과정을수행하여회수율및분석오차를산출하였다. effect- 수확일자별 amisulbrom 잔류량 ) 생물학적반감기및 pre-harvest residue limit(phrl) 산출 경시적으로채취한엇갈이배추시료중 amisulbrom 잔류분석값의평균치를단순 1차감쇄반응으로해석, 회귀식을최소자승법 (least square method) 으로산출한후감소계수로부터생물학적반감기를산출하였다 (Chae et al., 1981, Gomez et al., 1984). 회귀식의통계학적유의성을검정하기위해서상관계수의제곱인결정계수 (coefficient of correlation, r 2 ) 와분산분석을거쳐 F-검정을수행하였고, PHRL은국립농산물품질관리원에서규정한바에따라설정하였다. 즉, 감소상수인회귀계수에대하여 t-검정을수행, 유의성이인정되는회귀계수에대하여 95% 신뢰구간을구하고, 이중하한값을감소상수로결정하였다. 출하일의잔류량을식품공전허용기준으로대입한후출하전 10일까지의일별잔류량를추정, 산출하여 PHRL을설정하였다. 엇갈이배추중 amisulbrom 의희석효과수확일자별 amisulbrom의잔류농도와엇갈이배추무게변화를고려하여 dilution effect(a) 와 dilution effect를배제한 amisulbrom의잔류농도 (B) 를아래의식에의해산출하여잔류감소곡선을작성하였다. A=(0일차 amisulbrom 잔류량 0일차엇갈이배추무게 )/ 수확일자별엇갈이배추무게 B=0 일차 amisulbrom 잔류량 -( 수확일자별 dilution 결과및고찰 엇갈이배추재배중시설내의온 습도및엇갈이배추의증체율시험기간 10일동안의시설내기온은포장 1 및 2에서각각 , 범위였으며, 습도는각각 %, % 범위였다 (Fig. 1). 약제살포일로부터살포후 10일까지엇갈이배추의평균무게변화는포장 Fig. 1. Changes of temperature and humidity during cultivation of winter-grown cabbage.

5 124 Ahn et al. Fig. 2. Growth of winter-grown cabbage during experimental period. Table 4. Reproducibility of peak area and retention time of amisulbrom in HPLC Parameter Retention time (min) Peak Area (mau) Minimum Maximum Mean SD CV (%) *Abbreviations : SD, standard deviation; CV, coefficient of variance. Table 5. Recovery ratio of amisulbrom in winter-grown cabbage Pesticide Fortification (mg/kg) Recovery ratio (%) 1) SD CV (%) 1) Amisulbrom Mean values of triplicate samples with standard deviations. 1에서 0일차대비 44.5 g(53.4%), 포장 2에서는 0일차대비 42.7 g(50.6%) 증가한것으로확인되었다 (Fig. 2). 표준검량선의직선성및분석정량한계 Amisulbrom의농도별표준용액 ( mg/l) 20 μl 를 HPLC 에주입, 분석하여얻은검량선의회귀방정식은 y=29.63x-0.22(r 2 =0.9999**) 로우수한직선성을나타내었다. 분석기기의정량한계 (LOQ) 와시료량, 그리고분석과정중의농축배율을계상하여분석법의정량한계를산출하였다. 엇갈이배추시료에서간섭물질이존재하지않음을확인한후산출된 amisulbrom의정량한계는 0.04 mg/kg이었으며, 국제기준인 Codex(Codex Alimentarius Commission, 2003) 및식품의약품안전처 (Lee, 2009) 에서권장하는잔류농약분석법기준인 0.05 mg/kg 이하또는허용기준의 1/2 이하의정량한계기준에적합하였다. 분석기기의재현성 (Reproducibility) 평가분석기기의재현성평가를위해 0.5 mg/l의표준용액을 15번반복주입분석하여 retention time 및 peak area의변이계수 (CV, %) 를조사하여분석재현성평가를실시한결과, 조사된측정변수모두최대 2.7% 로높은분석재현성을나타내어기기분석시안정적이고재현성있는분석을수행할수있음을확인하였다 (Table 4). 분석법의회수율검증회수율검증을위해마쇄한무처리시료에 amisulbrom 표준용액을정량한계의 10 및 50배의농도가되도록첨가하고, 3반복분석하여회수율을검토하였다. 엇갈이배추시료용액의분석크로마토그램에서 amisulbrom의머무름시간은 8.2분이었으며, amisulbrom peak와중첩되는방해물질은없었다 (Fig. 3). 정량한계 10배수준에서는 93.7%, 정량한계 50배수준에서는 100.0% 의양호한회수율을보였고, 재현성

6 Establishment of PHRL of Amisulbrom on Winter-Grown Cabbage 125 A B C D Fig. 3. HPLC chromatogram of amisulbrom. A; standard(10.0 mg/l), B; control, C; recovery(5.0 mg/kg), D; a field sample. Fig. 4. Dissipation curves of amisulbrom in winter-grown cabbage during experimental period. 도양호하여분석오차는최대 2.5% 로조사되어처리수준에관계없이잔류분석기준인회수율 % 범위와분석오차 10% 이내를만족하였다 (Table 5). 엇갈이배추재배기간중잔류량변화농산물의재배기간중살포된농약의잔류량은약제의물리화학적특성, 제형, 기상, 약제처리방법, 재배조건, 약제살포후수확경과일수및작물체의생육으로인한생체량증가에의해영향을받는다 (Jeong et al., 2004). 엇갈이배추재배시살균제 amisulbrom 액상수화제를기준량으로 1회살포한후 10일동안시험농약의잔류량을측정하여약제의잔류양상을분석한결과, 초기잔류량은포장 1에서 8.16 mg/kg, 포장 2에서 7.43 mg/kg으로 MRL 인 2.0 mg/kg보다약 4배수준에해당하는수치를나타내었으나, 10일후에는포장 1과 2에서모두 1.27 mg/kg으로조사되어 MRL 이하로낮아졌다 (Fig. 4). Amisulbrom 의경시적잔류량감소경향을단순 1차감쇄반응으로해석, 회귀식을최소자승법 (least square method) 으로산출하였다. 상관계수의제곱인결정계수 (coefficient of correlation, r 2 ) 와분산분석을거쳐 F-검정을수행한결과, 두포장모두에서 amisulbrom의경시적잔류량변화에대한회귀식의통계학적유의성이 99% 수준에서인정되었고 (Table 6), 이회귀식에의해산출된 amisulbrom의재배기간중생물학적반감기는각각 3.7일과 4.1일이었다. 회귀계수에대한 t-검정의결과, 두포장모두에서 99% 수준에서통계학적유의성이인정되었다 (Table 6). 따라서국립농산물품

7 126 Ahn et al. Table 6. Regression for the dissipation of amisulbrom residues in winter-grown cabbage 1) 2) Field Regression curve r 2 F-test t-test Decay coefficient (day -1 ) Regression Min. of 95% confidence 2) Field 1 Y=8.936e X 0.985** 1) ** 16.35** Field 2 Y=7.172e X 0.993** ** 23.78** Significance at 95% (*) and 99% (**) probability. The lowest value of 95% confidence limit. Fig. 5. Dilution effect for the dissipation of amisulbrom during experimental period. Fig. 6. Pre-harvest residue limit of amisulbrom for winter-grown cabbage. 질관리원에서규정한바에따라회귀계수에대하여 95% 신뢰구간을 L=λ±t 0.05(n-1) (s/n 1/2 ) 식에의하여구하고, 이중하한값을 PHRL 산출을위한감소상수로결정하는것이가능하였다. 포장 1 및 2에서 95% 신뢰구간의하한값은각각 및 day -1 이었다. 엇갈이배추의증체율에따른 amisulbrom 의희석효과작물의농약잔류성에영향을주는가장큰요인중하나로작물의비대생장에따른약제의희석효과를들수있다 (Marin et al., 2003). 포장 1과 2의기준량처리시 amisulbrom 잔류감소곡선을기준으로하여엇갈이배추의무게증가에따른 amisulbrom의희석효과를배제한감소곡선을비교해보면두잔류감소곡선간의잔류량감소차이는크지않았다 (Fig. 5). 엇갈이배추는시험약제의살포시부터수확시까지비대생장이급격한작물이아니기때문에증체율에따른잔류농약의희석효과는오이 (Lee et al., 2008) 와같이급격히생장하는작물에비해크지않은것으로판단된다. Pre-harvest residue limit(phrl) 산출 PHRL은작물수확시농약잔류량이 MRL을초과하지않도록수확전일정시점의잔류량을설정한기준수치로써 amisulbrom의기준량살포시엇갈이배추중 amisulbrom 의잔류회귀식으로부터산출한회귀계수의 95% 신뢰구간중하한값을적용하였다. 즉, Table 6의 95% 신뢰구간중하한값을적용한회귀식은각각 Y=11.062e X 및 Y=10.288e X 이며, 이회귀식을이용하여 PHRL 곡선을작성하였다 (Fig. 6).

8 Establishment of PHRL of Amisulbrom on Winter-Grown Cabbage 127 생산단계농약잔류허용기준추천 PHRL 곡선을근거로하여엇갈이배추수확 10일전잔류량이 mg/kg 또는 5일전에 mg/kg 이하라면수확시 amisulbrom의잔류농도가 MRL 수준이하로잔류할것으로예측되어이를엇갈이배추에대한생산단계농약잔류허용기준을추천할수있을것이다. 요약 본연구에서는엇갈이배추재배기간중살균제 amisulbrom 을살포하고, 농약살포후 0(2시간이내 ), 1, 3, 5, 7 및 10일에엇갈이배추시료를채취하여 amisulbrom을분석하고 amisulbrom의생물학적반감기를산출하여생산단계농약잔류허용기준 (PHRL; Pre-Harvest Residue Limit) 을설정하였다. 엇갈이배추에잔류한 amisulbrom은 acetonitrile과 dichloromethane 으로각각추출및분배를진행하여 HPLC-UVD 로분석하였다. Amisulbrom의분석정량한계는 0.04 mg/kg 이었으며, 평균회수율은 0.4 및 2.0 mg/kg 의두수준에서각각 93.7±2.3% 와 100.0±1.3% 이었다. Amisulbrom 을기준량으로 1회살포시엇갈이배추중의생물학적반감기는포장 1 및 2에서각각 3.7일과 4.1일로계산되었으며, 증체량에따른희석효과가 amisulbrom의잔류량감소에주된인자로작용하지는않았다. 잔류감소회귀식을이용한생산단계농약잔류허용기준은수확 10일전 mg/kg, 또는 5 일전에 mg/kg 으로제안하였다. Acknowledgment This study was carried out with the support of Ministry of Food and Drug Safety(Project No.: ), Republic of Korea in References Bentson, K. P. (1990). Fate of xenobiotics in foliar pesticide deposits. In Reviews of Environmental Contamination and Toxicology, pp Springer New York. Chae, Y. A., Lee, Y. M., & Ku, J. O. (1981). Biological Statistics, pp , Jeongminsa, Seoul, Korea. Choi, K. I., Seong, K. Y., Jeong, T. K., Lee J. W., Hur, J. H., Ko, K. Y., & Lee, K. S. (2002). Dissipation and removal rate of dichlofluanid and iprodione residue on greenhouse cherry tomato, Korean Journal of Environmental Agriculture, 21(4), Gomez, K. A., & Gomex A. A. (1984), Statistical Procedures for Agricultural Research, 2nd ed., pp , John Wiley, New York, USA. Hill, B. D., & Inaba, D. J. (1990). Fate and persistence of residues on wheat used to explain efficacy differences between deltamethrin suspension concentrate and emulsifiable concentrate formulations. Pesticide Science, 29(1), Jeong, Y. H., Kim, J. U., Kim, J. H., Lee, Y. D., Lim, C. H., Hu, & J. H. (2004). Modern pesticide, pp. 5, , Sigma-press, Korea. Kim, S. W., Lee, E. M., Yang L., Park, H. W., Lee, H. R., Riu, M. J., Na, Y. R., Noh, J. E., Keum, Y. S., Song, H. H., & Kim, J. H. (2009). Establishment of pre-harvest residue limit (PHRL) of insecticide Bifenthrin during cultivation of grape. The Korean Journal of Pesticide Science, 13(4), Kim, Y. S., Park, J. H., Park, J. W., Lee, Y. D., Lee, K. S., & Kim, J. E. (2002). Persistence and dislodgeable residues of chlorpyrifos and procymidone in lettuce leaves under greenhouse condition, Korean Journal of Environmental Agriculture. 21(2), Ko, K. Y., Lee, Y. J., Won, D. J., Park, H. J., & Lee, K. S. (2003). Residual pattern of procymidone and bifenthrin in perilla leaf during the period of cultivation and storage, Korean Journal of Environmental Agriculture, 22(1), Lee, J. H., Park, H. W., Keum, Y. S., Kwon, C. H., Lee, Y. D., & Kim, J. H. (2008). Dissipation pattern of boscalid in cucumber under greenhouse condition. The Korean Journal of Pesticide Science, 12(1), Lee, S. J., Kim, Y. H., Song, L. S., Hwang, Y. S., Lim, J. D., Sohn, E. H., Im, M. H., Do, J. A., Oh, J. H., Kwon, K. S., Lee, J. K., Lee, Y. D., & Choung, M. G. (2011). Development of analytical method for Fenoxycarb, Pyriproxyfen and Methoprene residues in agricultural commodities using HPLC-UVD/MS. The Korean Journal of Pesticide Science, 15(3), Marín, A., Oliva, J., Garcia, C., Navarro, S., & Barba, A. (2003). Dissipation rates of cyprodinil and fludioxonil in lettuce and table grape in the field and under cold storage conditions. Journal of Agricultural and Food Chemistry, 51(16), MacBean, C. (2012). The Pesticide manual; A World Compendium, pp , 16th ed., British Crop Protection Council, Hampshire, UK. Seong, K. Y., Choi, K. I., Jeong, M. H., Hur, J. H., Kim, J. G., & Lee, K. S. (2004). Residue and half-lives of bitertanol and tebuconazole in greenhouse-grown pepper, Journal of the Korean Society for Applied Biological Chemistry, 47(1),

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