Korean Journal of Environmental Agriculture Korean J Environ Agric (2013) Online ISSN: 2233-4173 Vol. 32, No. 1, pp. 84-93 http://dx.doi.org/10.5338/kjea.2013.32.1.84 Print ISSN: 1225-3537 Research Article Open Access 파프리카재배기간중담배나방방제에사용되는살충제의잔류특성 이동열, 1 김영진, 1,2 김상곤, 3 강규영 1,3* 1 경상대학교응용생명과학부 (BK21 농생명산업글로벌인재육성사업단 ) & 경상대학교농업생명과학연구원, 2 동의과학대학교동의분석센터, 3 경상대학교식물생명공학연구소 Residual Characteristics of Insecticides Used for Oriental Tobacco Budworm Control of Paprika Dong Yeol Lee, 1 Yeong Jin Kim, 1,2 Sang Gon Kim 3 and Kyu Young Kang 1,3* ( 1 Divison of Applied Life Science (BK21 Program) & Institute of Agriculture and Life Science, Gyeongsang National University, Jinju, 660-701, Korea, 2 Dong-Eui Institute of Technology Dong-Eui Analysis Center, Dong-Eui Institute of Technology, Busan, 614-715, Korea, 3 Plant Molecular Biology and Biotechnology Research Center, Gyeongsang National University, Jinju, 660-701, Korea) Received: 12 February 2013 / Revised: 14 March 2013 / Accepted: 25 March 2013 c 2013 The Korean Society of Environmental Agriculture This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/by-nc/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited. Abstract BACKGROUND: This study was carried out to investigate the residual characteristics of insecticides used for Oriental Tobacco Budworm control and to establish the recommended pre-harvest residue limit leading to contribution in safety of paprika production. METHODS AND RESULTS: The recommended Pre- Harvest Residue Limits (PHRLs) of insecticides during cultivation of paprika were calculated from residue analyses of insecticides in fruits 1, 3, 5, 7, 10, 12, 15, 18 and 21 s after treatment. Paprika samples were extracted with QuEChERS method and cleaned-up with amino propyl SPE cartridge and PSA, and insecticide residues were analyzed either by HPLC/DAD or GLC/ECD. The limits of detection were 0.01 mg/kg for 5 insecticides. Average recoveries were 81.3±1.62%-98.3±1.58% of 5 insecticides at fortification levels of 0.1 and 0.5 mg/kg. * 교신저자 (corresponding author), Phone: +82-55-772-1961; Fax: +82-55-772-1969; E-mail: kykang@gnu.ac.kr The biological half-lives of the insecticides were 8.5 s for bifenthrin, 11.8 s for chlorantraniliprole, 16.8 s for chlorfenapyr, 7.1 s for lamda-cyhalothrin and 31.3 s for methoxyfenozide at recommended dosage, respectively. CONCLUSION(S): The pre-harvest residue limits for 10 s before harvest were recommended 1.05 mg/kg, 1.41 mg/kg, 0.93 mg/kg, 2.06 mg/kg and 1.08 mg/kg as bifenthrin, chlorantraniliprole, chlorfenapyr, lamda-cyhalothrin and methoxyfenozide, respectively. This study can provide good practical measures to produce safe paprika fruit by prevention of products from exceeding of MRLs at pre-harvest stage. Key Words: Biological half-lives, Insecticide, Oriental Tobacco Budworm, Paprika, Pre-Harvest Residue Limit 서론 농약은병해충및잡초로부터농산물을보호하고생산량증대와품질향상및수확한농산물의저장기간중손실을방지하는등다양한용도로광범위하게사용되고있으며현대농업 84
Residual Characteristics of Insecticides Used for Oriental Tobacco Budworm Control of Paprika 85 에필요한중요한농업자재로서이러한농약의사용은필수적이라할수있다 (Jeong et al., 2004; Hong et al., 2011). 하지만이러한농약은병해충및잡초를효과적으로방제하기위하여여러형태의화학구조를가지고있고, 본래의목적으로사용이끝난후에도환경조건등에따라농작물및환경중에잔류되는경우가발생하기도한다 (Kim et al., 2009). 이렇게농약이지나치게잔류된농산물을섭취하게될경우인체건강상의문제를유발할수있기때문에농작물중농약잔류허용기준 (Maximum Residue Limit; MRL, 단위 mg/kg) 을설정하여국제적, 국가적으로도관리감독하고있다 (Lim et al., 2011). 농약잔류허용기준을초과한농산물에대해서는출하연기, 용도전환, 현장계도및폐기처분등의조치가취해지지만, 잔류허용기준을초과한부적합농산물들은수확후신선도유지의어려움이있어실질적으로출하연기가불가능하고, 용도의전환및재활용의기회도거의없기때문에대부분의부적합농산물들은폐기처분되고있으며이로인한생산자의금전적손실이발생하고있다. 이러한문제점을해결하기위해서는농산물들의잔류농약에대한안전성평가가출하전에이루어지는것이바람직할것이고, 이를효율적으로운영하기위해서는출하시점의 MRL과농산물재배시살포되는농약의생물학적반감기에근거한생산단계에서의잔류농약허용기준이별도로설정되어야할것이다 (Lee et al., 2009a; Kim et al., 2002; Ko et al., 2004). 파프리카는 1994년국내에서처음으로재배된이후지속적으로재배면적과생산량이증가하고있으며 (Cho et al., 2011), 2011년기준재배면적은약 450 ha이고연간생산량은 40만톤수준에달하고있으며, 우리나라채소류수출전체 17,820만달러중 1/3이상인 6,590만달러의높은비중을차지하는고소득작물이다 ( 농수산물무역정보, 2012). 파프리카의과실은비대가끝나고난후착색기간에만 15 일전후가소요되고, 이시기에는무게증가에의한농약의상대적희석효과가크지않아수확전살포초기의잔류농도가출하일까지크게감소되지않을수있는위험이큰작물로서, 수확전생산단계에서농약사용에각별한주의가필요하다고할수있다. 시설내파프리카재배시발생하는주요해충중담배나방으로인한피해가발생하고있으며, 이해충은유충이잎, 꽃봉오리등을가해하기도하지만주로과실속에들어가종실을가해하여피해과실은대부분부패하여낙과하게되며계속다른과실로옮겨가서가해하여큰피해를일으키며 (Song et al., 2009), 이러한담배나방방제를위해여러가지살충제가사용되고있다. 본연구에서는담배나방방제를위해등록되어사용되는주요살충제인 bifenthrin, chlornatraniliprole, chlorfenapyr, lamda-cyhalothrin 그리고 methoxyfenozide를농가조사 를통하여선발한후 5개살충제의수확전잔류농도를예측하기위하여시험농약을시설내파프리카포장에살포하여경시적농약잔류특성을파악하고생물학적반감기를산출한후시험농약의잔류허용기준과비교하여그결과를생산단계에서농약잔류특성을알아보고자하였다. 재료및방법 시약및기구시험에사용된살충제의표준품들은 Dr. Ehrenstorfer사 ( 독일 ) 로부터구입한 bifenthrin ( 순도 99.5%), chlorantraniliprole ( 순도 94.5%), chlorfenapyr ( 순도 99%), lamda-cyhalothrin ( 순도 98%) 과 methoxyfenozide ( 순도 98%) 를사용하였고, 추출및정제를위해사용한 acetonitrile과 acetone은 Merck사 ( 독일 ) 에서구입하여사용하였으며, SPE 정제를위해사용한 amino propyl cartridge (MEGA BE-NH 2 SPE cartridge 1.0 g, 6 ml) 와 PSA (Primary Secondary Amine) 은 Agilent사 ( 미국 ) 에서구입하여사용하였다. 시험약제시험에사용한살충제의물리화학적특성및화학구조식은 Table 1과같고, 안전사용기준및잔류허용기준은 Table 2와같다. 시험작물및작물재배시험작물인파프리카 (Capsicum annuum var. angulosum Mill, cv. 스페셜 ) 는경상남도진주시대곡면소재시설농가에재배하고있는작물을사용하였다. 시험포장은길이 100 m 폭 3 m (300m 2 ) 면적에약제처리별파프리카 9주씩 3 반복으로시험구를배치하고, 완충구간으로 3주를두어교차오염을방지하였다. 또한 Thermo Recorder (Model TR-72U, T&D CORP, JAPAN) 를이용하여시험기간중시험포장의온도와습도를 1시간간격으로측정하였다. 농약살포, 시료채취및증체율조사농약의처리구는반복구간별로파프리카 9그루로설정하여작물의수확예정 21일전인 2011년 5월 30일, 4그룹열매가비대생장후아래쪽에서 2, 3번열매가착색이시작되는시점을택해배부식분무기를이용하여시험농약별로각각해당농약의안전사용기준에따라표준희석살포용액 ( 기준량 ) 과표준희석살포용액의 2배농도로제조한살포용액 ( 배량 ) 을작물에충분히흐를정도로구간별 5 L씩 1회살포하고, 처리후 1, 3, 5, 7, 10, 12, 15, 18 그리고 21일째시료및무처리구시료를구간별로 6개의시료를총 1 kg 이상채취하고 -20 에저장하였다.
86 LEE et al. Table 1. Physico-chemical properties and chemical structures of 5 insecticides used in this study (Tomlin, 2009) Insecticide Chemical structure Molecular Weight Vapor pressure (mpa) Kow bifenthrin 422.9 0.024 (25 ) logp>6 chlorantraniliprole 483.2 2.1 10-8 (20 ) logp=2.76 chlorfenapyr 407.6 <1.2 10-2 (20 ) logp=4.83 lamda-cyhalothrin 449.9 2 10-4 (20 ) logp=7 methoxyfenozide 368.5 <1.48 10-3 (20 ) logp=3.7
Residual Characteristics of Insecticides Used for Oriental Tobacco Budworm Control of Paprika 87 Table 2. Pesticide formulations, safe use guidelines, and MRLs of 5 insecticides (Korea Crop Protection Association, 2011) Insecticide formulation type A.I. a) (%) Dilution (g or ml in 20 L water) Safe use guidelines PHI b) () MAF c) (times) MRL d) (mg/kg) bifenthrin WP e) 2 5 g 7 3 0.5 chlorantraniliprole WG f) 5 10 g 3 3 1.0 chlorfenapyr SC g) 10 10 ml 3 3 0.7 lamda-cyhalothrin WP 1 20 g 5 3 1.0 methoxyfenozide SC 21 10 ml 7 3 1.0 a) Active Ingredient b) Pre-Harvest Interval c) Maximum Application Frequency d) Maximum Residue Limit e) Wettable Powder f) Water Dispersible Granule g) Suspension Concentrate 표준검량선작성시험농약인 bifenthrin, chlorfenapyr와 lamda-cyhalothrin 표준품은 acetone으로녹여 1,000 mg/l 농도로조제한 stock solution을 0.01, 0.05, 0.1, 0.2, 0.5, 1, 2, 5 mg/l농도로희석하여 1 μl 씩 GLC/ECD (Electron Capture Detector) 에, chlorantraniliprole 과 methoxyfenozide 표준품은 acetonitrile으로녹여 1,000 mg/l 농도로조제한 stock solution을 0.05, 0.1, 0.5, 1, 2, 5, 10 mg/l이되게희석하여 10 μl 씩 HPLC/DAD (Diode Array Detector) 에주입하여나타난크로마토그램상의피크면적을기준으로표준검량선을작성하였다. 잔류농약분석파프리카중잔류농약의추출은 QuEChERS법으로수행하였다 (Anastassiades et al., 2003; Lehotay, 2007). Conical centrifuge tube (50 ml) 에세절한열매 15 g을칭량하고, 여기에 0.1% CH 3COOH가되게첨가한 acetonitrile 15 ml, MgSO 4 6 g, CH 3COONa 1.5 g을처리한후 30분간진탕하여원심분리 (3000 rpm, 10 min, 4 ) 하고상등액 10 ml 를농축한후잔사물을 dichloromethane 5 ml 로용해하였다. Pre-washing 한 NH 2 SPE cartridge에 dichloromethane 용해액 5 ml를 loading하고 methanol/dichloromethane (v/v, 5/95) 를이용하여 20 ml로용출시킨후질소미세농축기로농축하였다. 농축된시료를 HPLC 분석용농약은 acetonitrile로 2 ml로, GLC 분석용농약은 acetone 10 ml로용해하여이중 1 ml을 PSA 50 mg과 MgSO 4 150 mg이처리된 E-tube로옮겨다시한번정제하였다. 정제후 0.2 μm filter로여과하여 HPLC/DAD와 GLC/ECD를이용하여분석하였으며, 기기분석조건은각각 Table 3, Table 4와같다. Table 3. HPLC/DAD conditions for the analyses of insecticides chlorantraniliprole and methoxyfenozide Instrument Column Detector Wavelength Flow rate Condition Injection volume Agilent 1200 series HPLC with auto sampler Agilent XDB-C18, 4.6 150 mm, 5 μm Diode Array Detector (DAD) 254 nm 1.0 ml/min Time (min) H 20 Acetonitrile Total (min) 0 70 30 5 70 30 5 20 0 100 20 25 0 100 25 10 μl
88 LEE et al. Table 4. GLC/ECD conditions for the analyses of insecticides bifenthrin, chlorfenapyr and lamda-cyhalothrin Instrument Column Detector Flow rate Column oven Split Injection volume Varian CP-3800 GLC with auto sampler DB-5, 30 m 0.25 mm i.d., 0.25 μm Electron Capture Detector (ECD) 1.0 ml/min Temperature ( ) Rate ( /min) Hold (min) Total (min) 150 5 5 280 10 10 28 Injection oven : 280, Detector oven : 280 Splitless 1 μl 회수율시험 회수율시험은재배기간중에시험약제를처리하지않은시료에각농약의표준용액을검출한계의 10배, 50배농도인 0.1와 0.5 mg/kg이되도록처리하고균일하게혼화하여상기잔류분석과정을수행하여회수율을산출하였다. 잔류농약의생물학적반감기및추천생산단계농약잔류허용기준의산출파프리카중잔류농약의생물학적반감기는 Microsoft사의 Microsoft Office Excel 2007의지수곡선식을이용하여산출하였다 (Lee et al., 2009b; Park et al., 2005). 또한추천생산단계잔류허용기준은각시험농약별로산출한회귀곡선식을이용하여산출하였다 (Park et al., 2011; Lee et al., 2008). 결과및고찰 검출한계및회수율시험상기시험분석법을수행한파프리카시료에서 5개살충제의머무름시간은 bifenthrin 13.1 min, chlorantraniliprole 13.0 min, chlorfenapyr 10.9 min, lamda-cyhalothrin 14.0 min 그리고 methoxyfenozide 6.3 min임을확인하였으며, 크로마토그램상에서 peak를방해하는물질은존재하지않았다 (Fig. 1). 시험분석법의검출한계는시험약제에서모두 0.01 mg/kg이었고, 분석법에의한시험농약의회수율시험결과는 0.1 및 0.5 mg/kg 수준에서식품의약품안전청에서권고하는회수율범위인 70-120%, 반복회수율수치간변이계수 20% 이하의기준과잘부합하여본연구에서사용한시험농약의잔류소장을구명하기에효율적인분석방법이라고판단된다 (Table 5). Table 5. Recovery rates and Limits of Detection(LOD) of the analytical methods a) b) Insecticide bifenthrin chlorantraniliprole chlorfenapyr lamda-cyhalothrin methoxyfenozide Fortification level (mg/kg) Recovery±CV a) (%) 0.1 95.2 ± 2.8 0.5 89.1 ± 1.6 0.1 81.3 ± 1.6 0.5 98.3 ± 1.6 0.1 94.5 ± 10.1 0.5 92.0 ± 3.5 0.1 93.0 ± 2.0 0.5 94.9 ± 2.3 0.1 84.9 ± 1.2 0.5 91.8 ± 10.6 Coefficient of variation = (standard deviation / average) 100 Limit of detection LOD b) (mg/kg) 0.01 0.01 0.01 0.01 0.01
Residual Characteristics of Insecticides Used for Oriental Tobacco Budworm Control of Paprika 89 A B C D E F G H I J K L M N O Fig. 1. chromatograms of bifenthrin(a : standard 0.5 mg/kg, B : control, C : recovery 0.5 mg/kg), chlorantraniliprole(d : standard 0.5 mg/kg, E : control, F : recovery 0.5 mg/kg), chlorfenapyr (G : standard 0.5 mg/kg, H : control, I : recovery 0.5 mg/kg), lamda-cyhalothrin(j : standard 0.5 mg/kg, K : control, L : recovery 0.5 mg/kg) and methoxyfenozide (M : standard 0.5 mg/kg, N : control, O : recovery 0.5 mg/kg). 파프리카시험포장의기상조건과증체율시험기간중시설내포장의평균온도의범위는 24.6-27.8 C 였고평균습도는 62.8-78.7% 를기록하였다. 또한, 약제살포후경과일자별파프리카의증체율은채취시료의무게를측정한후평균무게를산출하였고, 가장적은평균무게는 176.9 g이었고, 가장높은평균무게는 191.5 g으로시험기간중비대생장은거의일어나지않았으며각수확일자별평균무게는 Fig. 2와같이조사되었다.
90 LEE et al. Fig. 2. Average of paprika sample weight during experiment period. B 파프리카재배기간중잔류농도변화시험약제를살포한후 0( 살포 2시간후 ), 1, 3, 5, 7, 10, 12, 15, 18 그리고 21일에시료를채취하여잔류농도를계산한결과 bifenthrin 기준량살포와배량살포시잔류농도는각각 0.06-0.23 mg/kg, 0.17-0.32 mg/kg 수준이었고, chlorantraniliprole 기준량살포와배량살포시잔류농도는각각 0.02-0.06 mg/kg, 0.03-0.17 mg/kg 수준으로나타났으며, chlorfenapyr 기준량살포와배량살포시잔류농도는각각 0.19-0.47 mg/kg, 0.32-1.12 mg/kg 수준이었으며배량살포구간에서는처리후 4회조사구간에걸쳐 MRL인 0.7 mg/kg을초과하는구간이나타났다. lamda-cyhalothrin에서잔류농도는각각 0.01-0.06 mg/kg, 0.17-0.32 mg/kg 수준이었으며두약제는시험기간동안 MRL을초과하는구간은나타나지않았다. 그리고 methoxyfenozide 기준량살포와배량살포시잔류농도는각각 0.38-0.58 mg/kg, 0.12-1.27 mg/kg 수준이었으며배량살포구간에서는처리후 2회조사구간에걸쳐 MRL인 1.0 mg/kg을초과하는구간이나타났다 (Fig. 3). C D A E Fig. 3. Dissipation curves of bifenthrin (A), chlorantraniliprole (B), chlorfenapyr (C), lamdacyhalothrin (D) and methoxyfenozide (E) in paprika.
Residual Characteristics of Insecticides Used for Oriental Tobacco Budworm Control of Paprika 91 파프리카증체율에의한시험살충제의희석효과 농약의작물잔류에영향을미치는주요인자로과실의비대생장에따른희석효과를들수있다 (Lee et al., 2012). 시험기간중파프리카의평균무게는수확초기부터마지막까지순차적으로증가하지않았으며, 최소 176.9 g, 최대 191.5 g으로 6.5% 의적은차이를나타내었다. Cho et al. (2011) 은파프리카열매는수확 2주전후에과중의변화가거의없이착색에소요되는성숙과정이나타난다고보고하였고, 이로미루어보아애호박 (Park et al., 2011), 오이 (Lee et al., 2008) 와같이시험기간중중량증가가급격하게일어나는작물에비해비대생장에의한잔류농약의희석효과는거의나타나지않을것으로판단된다. 잔류농약의생물학적반감기및생산단계잔류허용기준의산출시험살충제의기준량처리와배량처리구간에서잔류감소회귀식과생물학적반감기는 Table 6과같은결과를나타내었다. bifenthrin의경우 8.5일과 20.9일로나타났으며이는 Lee et al. (2009a) 에서호박중의 1.8일, 1.5일과 Kim et al. (2007) 에서배추중의 2.5일, 3.1일보다긴생물학적반감기를나타내었다. 하지만포도의경우각각 21일과 23일로산출되었으며 (Kim et al., 2009), 파프리카보다긴생물학적반감기를나타내었다. chlorantraniliprole의경우 11.8일과 6.4일로조사되었고, chlorfenapyr의경우 16.8일과 11일로나타났으며이는취나물에서 Lim et al. (2011) 이보고한 3.5 일, 3.4일보다긴생물학적반감기를나타내었다. lamdacyhalothrin의경우 7.1일과 20.9일이었으며이는 Kim et al. (2007) 에서배추중의 3.6일, 3.9일과 Yoon et al. (2008) 에서 1.7일, 1.8일보다긴생물학적반감기를나타내었다. 그 리고 methoxyfenozide 의생물학적반감기는 31.3 일과 24.9 일로각각나타났으며이는취나물에서 Hong et al. (2011) 이보고한 3.99일, 5.98일보다긴생물학적반감기를나타내었다. 시험약제살포시점부터수확까지비대생장이급격하게일어나는작물인호박, 배추, 상추, 취나물등에서의생물학적반감기는파프리카에서보다짧게나타났으며, 포도와같이비대생장이크지않은작물에서는파프리카와비슷하거나긴생물학적반감기를가지는것으로보아작물의비대생장에의한농약의상대적희석효과가생물학적반감기에큰영향을미친다고할수있다. 파프리카에서는시험살충제중 chlorantraniliprole, chlorfenapyr와 methoxyfenozide 소실곡선에서는기준량처리보다배량처리구간에서짧은생물학적반감기를나타내고있고, bifenthrin과 lamdacyhalothrin 소실곡선에서기준량처리구간보다배량처리구간에서긴생물학적반감기를나타내고있다. 생산단계잔류허용기준의설정은수확시에잔류농도가 MRL을초과하지않도록수확전일자별잔류농도를설정한수치로서 (Lee et al., 2012) Table 7과같이생산단계잔류허용기준을설정하였다. 본연구를통해설정된생산단계잔류허용기준은각각수확 10일전잔류농도가 bifenthrin 1.05 mg/kg, chlorantraniliprole 1.41 mg/kg, chlorfenapyr 0.93 mg/kg, lamda-cyhalothrin 2.06 mg/kg 그리고 methoxyfenozide 1.08 mg/kg이면수확시잔류농도가 MRL이하로잔류할것으로예측된다. 파프리카재배중담배나방방제에사용되는농약에따라생산단계잔류허용기준을적용하여출하시의잔류농도를예측하여출하시기를조절함으로써 MRL을초과하지않는안전한파프리카를생산하여유통이가능할것으로기대된다. Table 6. Regression equations and biological half-lives of insecticides Insecticide Application dosage Regression equation Biological half-life bifenthrin Recommended y=0.3070e -0.0815x 8.5 Double y=0.3348e -0.0332x 20.9 chlorantraniliprole Recommended y=0.0767e -0.0589x 11.8 Double y=0.3168e -0.1088x 6.4 chlorfenapyr Recommended y=0.4833e -0.0413x 16.8 Double y=1.3160e -0.0063x 11.0 lamda-cyhalothrin Recommended y=0.0918e -0.0970x 7.1 Double y=0.3348e -0.0332x 20.9 methoxyfenozide Recommended y=0.5634e -0.0221x 31.3 Double y=1.2724e -0.0280x 24.9
92 LEE et al. Table 7. Recommended pre-harvest residue limit of 5 insecticides in paprika (mg/kg) Insecticide MRL Regression (mg/kg) coefficient 10 9 8 Pre-harvest residue limit (mg/kg) 7 6 5 4 3 2 1 Harvesting bifenthrin 0.5 0.0746 1.05 0.98 0.91 0.84 0.78 0.73 0.67 0.63 0.58 0.54 0.5 chlorantraniliprole 1.0 0.0345 1.41 1.36 1.32 1.27 1.23 1.19 1.15 1.11 1.07 1.04 1.0 chlorfenapyr 0.7 0.0280 0.93 0.9 0.88 0.85 0.83 0.81 0.78 0.76 0.74 0.72 0.7 lamda-cyhalothrin 1.0 0.0724 2.06 1.92 1.78 1.66 1.54 1.44 1.34 1.24 1.16 1.08 1.0 methoxyfenozide 1.0 0.0075 1.08 1.07 1.06 1.05 1.05 1.04 1.03 1.02 1.02 1.01 1.0 요약 본연구는파프리카재배중담배나방방제에사용되는살충제의잔류특성을알아보고추천생산단계잔류허용기준 (Pre-Harvest Residue Limit, PHRL) 설정을통하여안전한파프리카생산에기여하고자수행되었다. 파프리카에각각의농약을기준량처리와배량처리로살포한후 1, 3, 5, 7, 10, 12, 15, 18 그리고 21일에일정한간격에맞추어파프리카시료를수확하여잔류농약을분석하고생물학적반감기를산출한다음추천생산단계잔류허용기준 (Pre-Harvest Residue Limit, PHRL) 을설정하였다. 시료들은 QuEChERS법으로추출한후 NH 2 SPE cartridge와 PSA을이용하여정제하고 HPLC/DAD와 GLC/ECD를이용하여기기분석을하였다. 5개살충제의검출한계는모두 0.01 mg/kg 이며회수율은검출한계의 10배, 50배농도인 0.1, 0.5 mg/kg 가되도록 3반복처리하여 81.3±1.62% 에서 98.3±1.58% 였다. 시험살충제의생물학적반감기는 bifenthrin에서 11.8일, chlorantraniliprole 은 8.5일, chlorfenapyr 는 16.8일, lamda-cyhalothrin은 7.1 일, methoxyfenozide에서 31.3일로나타났다. 생산단계농약잔류허용기준은수확 10일전 bifenthrin, chlorantraniliprole, chlorfenapyr, lamda-cyhalothrin 그리고에서 methoxyfenozide 에서각각 1.05 mg/kg, 1.41 mg/kg, 0.93 mg/kg, 2.06 mg/kg 그리고 1.08 mg/kg으로제안하였다 감사의글 This research was supported by Technology Development Program for Agriculture and Forestry, Ministry for Food, Agriculture, Forestry and Fisheries, Republic of Korea. Authors gave thanks to ipet (Korea Institute of Planning and Evaluation for Technology in Food, Agriculture, Forestry and Fisheries) for their research grant. 참고문헌 Anastassiades, M., Lehotay, SJ., Stajnbaher, D., Schenck, FJ., 2003. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and dispersive solidphase extraction for the determination of pesticide residues in produce, J. AOAC Int. 86(2), 412-431. Cho, K.S., Lee, S.J., Lee, D.Y., Kim, Y.J., Choe, W.J., Lee, J.B., Kang, K.Y., 2011. Pre-harvest residual characteristics of boscalid and pyraclostrobin in paprika at different seasons and plant part, Korean J. Pestic. Sci. 15(3), 269-277. Hong, J.H., Lim, J.S., Lee, C.R., Han, K.T., Lee, Y.R., Lee, K.S., 2011. Study of pesticide residue allowed standard of methoxyfenozide and novaluron on Aster scaber during cultivation stage, Korean J. Pestic. Sci. 15(1), 8-14. Jeong, Y.H., Kim, J.U., Kim, J.H., Lee, Y.D., Lim, C.H., Hur, J.H., 2004. Modern pesticide, PP. 5, 339-342, first ed, Sigma press, Korea. Kim, D.K., Kim, J.K., Lee, E.Y., Park, I.Y., Noh, H.H., Park, Y.S., Kim, T.H., Jin, C.W., Kim., K.I., Yoon, S.S., Oh, S.K., Kyunh, K.S., 2007. Residual characteristics of some pyrethroid insecticides in korean cabbage, Korean J. Pestic. Sci. 11(3), 154-163. Kim, S.W., Lee, E.M., Lin, Y., 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, Korean J. Pestic. Sci. 13(4), 241-248. Kim, Y.S., Park, J.H., Park, J.W., Lee, Y.D., Lee, K.S., Kim, J.E., 2002. Persistence and dislodgeable of chlorpyrifos and procymidone in lettuce leaves under greenhouse condition. Korean J. Environ. Agri. 12(2), 149-155. Ko, K.Y., Kim, K.H., Lee, K.S., 2004. Residual pattern of procymidone and chlorothalonil in grape during the period of cultivation and storage, Korean J. Environ. Agri. 23(1), 47-51. Lee, D.Y., Kim, Y.J., Lee, S.J., Cho, K.S., Kim, S.G., Park, M.H., Kang, K.Y., 2012. Establishment of pre-harvest residue limit of fungicides pyrimethanil and trifloxystrobin
Residual Characteristics of Insecticides Used for Oriental Tobacco Budworm Control of Paprika 93 during cultivation of persimmon, Korean J. Environ. Agri. 31(1), 45-51. Lee, E.Y., Kim, D.K., Park. I.Y., Noh, H.H., Park, Y.S.., Kim, T.H., Jin, C.W., Kim, K.I., Yoon, S.S., Oh, S.K., Kyung, K.S., 2008. Korean J. Environ. Agri. 27(1), 92-98. Lee, E.Y., Noh, H.H., Park, Y.S., Kang, K.W., Kim, J.K., Jin, Y.D., Yun, S.S., Jin, C.W., Han, S.K., Kyung. K.S., 2009b. Residual characteristics of etofenprox and methoxyfenozide in chinese cabbage, Korean J. Pestic. Sci. 13(1), 13-20. Lee, E.Y., Noh, H.H., Park, Y.S., Kang, K.W., Lee, K.H., Lee, J.Y., Park, H.K., Yun, S.S., Jin, C.W., Han, S.K., Kyung. K.S., 2009a. Residual characteristics of bifenthrin and imidacloprid in squash, Korean J. Pestic. Sci. 13(2), 79-86. 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, Korean J. Pestic. Sci. 12(1), 67-73. Lim, J.S., Hong, J.H., Lee, C.R., Han, K.T., Lee, Y.R., Lee, K.S., 2011. Establishment of pre-harvest residue limit(phrl) of insecticide chlorfenapyr and fungicide fenarimol during cultivation of chwinamul(aster scabar), Korean J. Environ. Agri. 30(1), 52-59. Lehotay, SJ., 2007. Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaborative study. J. AOAC Int. 90(2), 485-520. Park, D.S., Seong, K.Y., Choi, K.I., Hur, J.H. 2005. Field tolerance of pesticides in the strawberry and comparison of biological half-lives estimated from kinetic models, Korean J. Pestic. Sci. 9(3), 231-236. Park, H.K., Noh, H.H., Lee, K.H., Lee, J.Y. Park, Y.S., Kang, K.W., Lee, E.Y., Yoon, S.S. Jin, C.W., Kyung, K.S. 2011. Residual characteristic of chlorpyrifos in squash and estimation of its residue before harvest, Korean J. Pestic. Sci. 15(4), 463-470. Song, Y.H., Kim, H.K., Kang, K.Y., Jeong, B.K., Lee, K.S., 2009. Interated Pest Management in pepper and paprika, pp. 181-185, first ed, Paprika research center, Korea Tomlin, C.D.S., 2009. The pesticide manual: A world compendium, pp. 104-105, 175-176, 180-181, 269-270, 764-765, fifteenth ed, BCPC, UK. Yoon, S.S., Shim, S.W., Kim, K.I., Ahn, M.S., Yoon, T.H., Kim, Y.J., Hwang, H.S., Jin, C.W., Han, S.K., Oh, S.K., Shin, J.H., Jin, Y.D., Lee, E.Y., Kyung, K.S., 2008. Residual characteristics of lamda-cyhalothrin and deltamethrin in lettuce, Korean J. Pestic. Sci. 12(2), 148-154.