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J. Fd Hyg. Safety Vol. 24, No. 1, pp. 27~37 (2009) Journal of Food Hygiene and Safety Available online at http://www.foodhygiene.or.

1 J. Fd Hyg. Safety Vol. 24, No. 1, pp. 27~37 (2009) Journal of Food Hygiene and Safety Available online at 서울강북지역유통농산물중농약잔류실태조사 박성규 * 하광태 김성단 김시정 이윤정 이경아 장정임 정삼식송부용 조석주 조한빈 최병현 김민영서울시보건환경연구원 Survey on Pesticide Residues in Commercial Agricultural Products in the Northern Area of Seoul Sung-Kyu Park*, Kwang-Tae Ha, Sung-Dan Kim, Si-Jung Kim, Yun-Jung Lee, Kyeong-Ah Lee, Jung-Im Jang, Sam-Sik Jeong, Bu-Young Song, Suk-Ju Jo, Han-Bin Jo, Byung-Hyum Choi, and Min-Young Kim Seoul Health & Environment Research, Seoul , Korea (Received September 12, 2008/Revised January 16, 2009/Accepted February 18, 2009) ABSTRACT - In an effort to evaluate the currents in pesticide residues, 3,020 agricultural products were tested by multiresidue method with 260 pesticides, obtained from the circulation market of in the Gangbuk province in %(616/3020) of the products were determined to contain pesticides residues, but only 4.1%(124/3020) of these were deemed to be unsuitable by the korea Food Code. Unsuitably products were spinach(21.0%), perilla leaf(17.3%), ulgari(13.6%), leek(12.4%), crowndaisy(12.4%), asterscaber(12.4%), chard(11.1%). Detected pesticides were procymidone(3.9%), endosulfan(2.6%), chlorfenapyr(2.2%), bifenthrin (1.3%), cypermethrin(0.7%), metalaxyl(0.9%), azoxystrobin(0.3%) and chlorothalonil(0.7%). Sixty-four pesticides were detected and 11 pesticides were newly detected in Thirty-one pesticides in agricultural products exceeded their MRLs. Key words: pesticide residues, agricultural products 농작물의생산성증대, 품질향상, 병해충방제및노동력절감등의이유로농약의사용량이증가하여농약의안전사용기준및환경보전의측면에서의농약의잔류허용량을설정하고있고 1), 농약의사용으로인한안전성확보차원에서안전성농약을개발하고있으며 2), 앞으로도이상적인농약, 즉목적하는효과를발휘하면서저독성, 선택독성, 환경조화, 잔류성이고려된적절한개발 실용화가진행되어갈것이다 3). 지구상에는인구에필요한식량의두배이상이존재하나전체의수급형태가언제까지안정적으로존재할수있는가하는문제와함께날로악화해가는환경문제도장래의식량문제에있어서간과할수없는부분이다. 이러한이유로어려운환경에서생산을극대화하고재해에의한손실을줄이고자하는연구를계속되고있다. *Correspondence to: Park-Sung Kyu, Seoul Metropolitan Government Research Institute of Public Health & Environment #202-3, Yangjae-dong, Seocho-gu, Seoul, , Korea Tel: Fax: psk94@seoul.go.kr 수확된농산물중의농약잔류로인한인체위해가능성때문에대부분의선진국에서는자국및수입농산물에대한잔류농약모니터링을매년실시하고있는실정이다. 미국에서는 FDA(Food & Drug Administration) 주관으로농산물에대한잔류농약모니터링을매년실시하여 4) 그보고서를공개하고있으며, 유럽의경우도각국의사정에따라대상농약과시료를자유로이선택되어모니터링을실시하고있고 5), 일본에서는국립의약품식품위생연구소외에지방의약품식품위생연구소의협력을얻어전국적으로잔류농약실태조사를실시하고있다 6). 우리나라는 1968년부터잔류허용기준 (maximum residue limit, MRL) 모니터링을실시한이후모니터링규모가커지게되면서조사대상농약및품목이점차확대되었다 7). 본연구는전보 8) 에이어 2007년 1년간의서울시강북지역에유통된농산물을대상으로농약의잔류량을검사하여잔류허용기준을초과하는작물은사전에차단하여농산물안전성확보와농민의농약에대한안전하고효과적인사용을추진하기위한기초자료로활용하고자수행하였다. 27

2 28 Sung-kyu Park et al. 재료및방법 시료및분석농약 2007년도 1월부터 12월까지서울강북지역 ( 백화점, 대형할인점, 재래시장 ) 에서유통되고있는상추등 145종 3,020 건을각 3kg씩을수거하여프로시미돈등잔류농약 260 종을분석하였다. 시료전처리는식품공전 83번다종다성 분농약동시시험법으로시험하였고분석흐름도는 Fig. 1에실험대상이된농산물의분류는 Table 1과같으며기기분석조건은 Table 2, 3에제시하였다. 시약및분석기기잔류농약분석용표준품은 Dr. Ehrenstorfer (Germany) 및 Chem service(usa) 제품을사용하였고염화나트륨은 Fig. 1. Flow chart of multiresidue method. Table 1. List of analyzed Agricultural Crop group (Number of Samples) Leafty vegetable(1545) Green & Fruit(594) Leave-stem vegetable(311) Fruit(174) Root(104) Grain(30) Mushroom(120) Photoe(38) Nut(8) Others(96) Total(3020) Product Name (Nltural Productsumber of Samples) Leafty lettuce(243), Spinach(136), Perilla leaf(127), Chinese Cabbage(96), Young radish(79), Ulgary(78), Broccoli(69), cabbage(68), Crown daisy(67), Pak-choi(65), Chard(43), Chard(43), Chicory(42), A.scaber(40), Juckchae(33), Leaf mustard(29), Romane(22), Pimpinella(22), Bomdong(22), Amaranth(19), Kale(14), Chicon(14), Ssamchoo(13), Cauliflower(13), Okrip(11), Butterbur(9), Mallow(9), Angelica(9), Vitamine(8), Lolla rossa(7), Danggui(7), Saengchae(5), Beet(5), Newgreen(4), Pepper leaf(3), Pumpkin leaf(3), Others(68) Pepper(150), Cucumber(151), Squash(111), Egg plant(58), Pimentos(53), Tomato(42), Paprica(18), Musk melon(7), Others(4) Weish onion(70), Leek(76), Dropwort(67), Bracken(21), Dolnamul(19), Gosari(19), Celery(17), Kohlrabi(6), Wild garlic(9), Sweet photostalk(3), Others(4) Strawberry(26), Banana(23), Grape(18), Persimon(15), Apple(12), Kiwi(9), Peach(9), Orange(6), Pear(5), Pineapple(2), Others(49) Radish(root)(59), Onion(9), Bonnet bellflower(9), Carrot(4), Garlic(4), Beat(4), Others(15) Rice(12), Barley(4), Corn(4), Foxtail millet(4), Other(10) Saesong-i mushroom(54), Oyster mushroom(27), Winter mushroom(27), Pine mushroom(3), Others(9) Sweet potatoes(17), Photoes(21) Peanuts(8) Bean (16), Bean sprout(4), Greenbean sprout(6), Tea(40), Others(30)

3 Survey on Pesticide Residues in Commercial Agricultural Products in the Northern Area of Seoul 29 Table 2. Analytical conditions of GC-ECD, GC-NPD, and GC-MSD GC-ECD GC-NPD GC-FPD GC-MSD HP-1701 HP-1701 Column (30m 0.32mm 0.25µm) (30m 0.32mm 0.25µm) HP-1 HP-5MS HP-5 HP-5 (30m 0.32mm 0.25µm) (30m 0.25mm 0.25µm) (30m 0.32mm 0.25µm) (30m 0.32mm 0.25µm) Gas Flow N 2 (1ml/min) N 2 (1.4ml/min) Air(60ml/min) H 2 (3.5ml/min) N 2 (0.9ml/min) Air(ml/min) H 2 (75ml/min) He(1ml/min) Inj. Temp. 230 o C 210 o C 210 o C 230 o C Det. Temp. 280 o C 270 o C 250 o C 280 o C(Interface Temp.) Oven Temp. 150 o C(1min)-12 o C/min- 240 o C(2min)-10 o C/min- 280 o C(11min) 110 o C(1min)-15 o C/min- 200 o C(8min)-10 o C/min- 260 o C(7min) 110 o C(1min)-15 o C/min- 200 o C(8min)-10 o C/min- 260 o C(8min) o C(2min)-10 o C/min- 280 o C(15min) Table 3. Analytical conditions of HPLC and LC-MSD HPLC-FLD HPLC-DAD LC-MSD Column Waters carbamate analysis column( mm) Zobax C8 Eclipse XDB-C18 Detector Scanning Fluorescence detector Diode Array and Multiple Wavelength Detectors Mass selective detector Wavelength Ex λ:339nm Em λ:445nm 200nm 200nm ~ 400nm Mobile Phase A : 12% MeOH B : MeOH:AcCN:Water(35:35:30) A : 90% Acetonitrile B : Water A : 12% Methanol B : MeOH:AcCN:Water(35:35:30) Flow rate 0.9ml/min 1.0ml/min 1.0ml/min Injection Vol. 20µl 10µl 20µl Time(min) A(%) B(%) Time(min) A(%) B(%) Time(min) % B Flow Gradient Program ml 1.5ml 1.5ml 1.5ml Tedia Company(USA) 제품을 Acetonitrile 등일반시약은잔류농약분석용및 HPLC용을사용하였다. 전처리에필요한 SPE-Florisil(8B-S013HCH, Phenomenex, USA) 를, HPLC는 SPE-NH 2 (8B-S009 JCH, Phenomenex, USA) 를사용하였다. 분쇄기 (Blixer 5 pius, robot Coupe, France), 균질기 omni, us/omi Macro, USA), GC/ECD(Agilent 6890, USA), GC/ MSD(Agilent 5973, USA), HPLC/DAD(Agilent 1 series, USA), HPLC/CAS(Waters, Alliance M2695+M2475, USA) 를사용하였다. 실험방법시료전처리는전보 9) 의다종다성분농약동시시험법에따라시료를균질화한후 50 g를잔농용 Acetonitrile으로 2 분간추출하고 Nacl을넣은밀크병에 filter로여과후 30 분정체후상층의 Acetonitrile 10 ml 시험용액으로사용 하였다. 유기인계농약성분은 02.µm nylon filter로여과후분석하였으며, 유기염소계농약은 20% Acetone/Hexane 용매를사용하여 Florisil SPE 로여과후분석하였으며, 카바메이트농약은 NH 2 SPE에!% MeOH/DCM의용매를사용하였다, 분석장비로는 GC-ECD, GC-NPD, GC-FPD를이용하여 198종농약성분을 HPLC-FLD, HPLC-UVD를이용하여 62종농약을분석하였으며, 검출된농약성분의정성확인에는 GC-MSD(Hewlett Packard , USA), LC-MSD SL(Agilent, USA) 를사용하였다. 결과및고찰 시료채취는 2007년 1월 ~12월부까지강북지역소재시장, 할인마트, 백화점, 대형슈퍼등에서유통되는농산물 145종 3,020건을구입하여 260종의잔류농약을다종다성분농약동시시험법으로분석한결과농산물에따른잔류허

4 30 Sung-kyu Park et al. Table 4. List of pesticides exceeded their MRLs in agricultural products Commedity No. of samles Pesticide No. of samples detected detected Leafy vegetable(717) Perilla.leaf 127 Lettuce 243 Mallow 9 Spinach 136 Chard 43 Commedity No. of samles Pesticide detected Leafy vegetable(159) Detection Range (mg/kg) MRL * (mg/kg) Kresoxim-methyl Procymidone Diethofencarb Fludioxonil , Chlorpyrifos-methyl , Iprobenfos Dimethomorph diniconazole Fenpyroxymate Endosulfan Fenpropathrin , Azoxystrobin Diethofencarb Carbendazim Metalaxyl Dimethomorph , Azoxystrobin Chlorpyrifo Pencycuron Endosulfan , Fludioxonil Pencycuron Diazinon Pyridaryl Dimethomorph Fludioxonil Azoxystrobin Ethaboxan Chlorfenapyr Spiromecifen Procymidone Fludioxonil Cypermethrin Ethaboxan Ethoprophos Dimethomorph Carbendazim Paclobutrazol Azoxystrobin No. of samples detected Detection Range (mg/kg) MRL * (mg/kg)

5 Survey on Pesticide Residues in Commercial Agricultural Products in the Northern Area of Seoul 31 Azoxystrobin , Chlorpyrifos , Kresoxim-methyl Diazinon A.scaber 40 Diethofencarb Flutolanil Pyridaryl Spiromecifen , Vinclozolin Azoxystrobin Bifenthrin Ulgary 78 Diazinon , Dimethomorph ~ Flutolanil , Kresoxim-methyl Chlorfenapyr Amaranth 19 Chlorothalonil Pencycuron Azoxystrobin , Chlorpyrifos Pyridaryl Azoxystrobin Kresoxim-methyl , Pimpinella 22 Flutolanil Diazinon Spiromecifen Diethofencarb Vinclozolin Stalk and stem vegetables(174) Procymidone ~ Chlorothalonil Leek 76 Pencycuron Bifenthrin Flutolanil Carbendazim Fluquinconazole W. onion 70 Propamocarb Endosulfan Procymidone W.garlic 9 Tebuconazole ~ Sedum 19 Pencycuron Fruiting vegetable(242) Chlorpyrifos Pepper 242 Hexaconazole Endosulfan Phenthoate

6 32 Sung-kyu Park et al. Stone fruit Root and tuber vegetable(54) Radish(root) 54 Chlorpyrifos Bifenthrin , Hexaconazole , Endosulfan Other plants(40) Green Tea 40 Fenvalerate , 용기준을초과한농약검출양은 Table 3과같다. 연도별농약검출빈도는 Table 5에서와같이 Procymidone 이전체검출량의 22.9%(119건 ) 로써 2006년도에이어높았으며, Endosulfan 15.2%(79건 ), chlorfenapyr 12.7%(66건 ), bifenthrin 7.5%(39건 ), cypermethrin 6.2%(32건 ) 순이었다. 2007년에는 boscalid, pyridarly, lufenuron, paclobutrazole, thiamethoxam, spiromecifen이처음으로기준을초과검출되었으며, spiromecifen은테트로닉에시드 (tetronic) 계통의살충제로서해충의지질생합성을저해해살충효과를보이며, 기존다른계통살충제에저항성이생긴해충에도우수한효과가있어약충, 알및성충에도붙임효과가있어병해충종합관리 (IPM) 에적합하여약제사용이증가하고있다. 잔류허용기준을초과하여나타난농산물은 64종 124 건으로 Table 5에서와같이 2000년이후지속적인증가율을보이고있으며, 허용기준을초과하지는않았으나농약이검출된경우는 2006년 470건에서 2007년 616건으로증가하였다. 2007년도에는 fenpropathrin, lufenuron, paclobutrazole, pencycuron, thiamethoxam, spiromecifen 등농약이새로이검출되었으며, 2006년도 54종보다많은 64종의농약이검출되었고 2002년도 36종검출이후로지속적으로증가하고있으며, 2007년도에는검출율이 616건 (20.4%) 으로 1999년 80건 (5.0%) 보다 7배이상증가하였다. 이는새로운농약의공급과사용하는농약의종류가다양화되고분석기술의향상과잔류농약허용기준의강화및농약성분에있어유효등록작물이외에서검출되면부적합것으로기준규격이강화 ( 식품의약품안전청고시제 호,63호) 되어이것이부적율을높아지게한원인으로보여진다 11). 2007년도에는 Fig. 2에서와같이 azoxystrobin, dimethomorph 과 Flutoranil이부적합빈도가높고, Table 6에서는잔류농약의검출율변화가 2006년도에이어지속적으로증가되고있으며, 2007년도에는농산물이도 소매점에서판매전에검사하는출하전검사확대로두배이상의검출율과부적율을나타내고있다. 기준초과농산물은시금치 (21.0%), 깻잎 (17.3%), 얼갈이 (13.6%), 부추 (12.4%) 순으로고추처럼농약을사용하지않으면감수율이높은작물이면서저독성의농약을지속적으로사용하는작물의특성을제외한검출빈도와기준초과농산물과비슷한경향을보이고있다. Fig. 7에서는농산물분류별검출율에서는엽채류 (11.3%), 과채류 (4.4%), 엽경채류 (2.0%) 감귤류 (0.5%) 순으로엽채류와과채류가평균부적율 4.1% 보다높게검출되어상대적으로농약사용이많음을알수있으며, 2007년도새로추가된농약 Spiromecifen은유기염소계살충제로담배나방및토양해충방제용으로사용하며환경호르몬으로분류되어있고수질오염성농약으로지정되어있어사용을규제하고있으며, 잔류성이길어생식하는엽채류나과채류에서의사용은피하고근채류에서도마찬가지로사용을금하고있는농약이다. Table 1의농산물분류에따라엽채류는 37종 1,545을검사하여 342건의농약이검출되어 22.1% 의검출율과 23 종 102건 (6.6%) 에서농약허용기준이상검출되었으며, 엽경채류는 14종 311건에서검사하여 7종 60건에서잔류농약이검출되어 19.4% 검출율과 4종 18건에서잔류허용기준을초과하여 5.8% 의부적율을나타내었다. 과채류는 12 종 594건을검사하여 10종 133건에서잔류농약이검출되어 22.4% 의검출율을보였고, 이중 1종 2건이잔류허용기준을초과하여 0.3% 의부적율을보였다. 그외곡류나두류, 버섯류에서는농약이검출되지않아최근수년간의경향과비슷하였다. 채소류에서는달래와머위가 9건중에서 3건에서기준이초과되어 33.3% 로가장높았고, 취나물이 40건을검사하여 10건에서기준이초과되어 25% 의부적율을나타냈다, 또한전년도에이어비름나물도 19건을검사하여 21.1% 의높은부적율을나타내고있으며, 부추, 깻잎, 쑥갓, 얼갈이등에서도 10% 이상의높은부적율을나타났다. 파, 근대, 머위에서는부적율의증가는분석기술의향상과허용기준의강화와농약성분의유효등록작물이외에서검출되면부적합것으로기준규격이강화되어부적율과검출율이높아지게되는원인 11) 으로볼수있고머위, 케일, 달래등에서는검출농약중에서 75% 이상의부적율이나타나는반면에고추에서는부적율이 3% 인것이특이할만한사항이었다. 고추에서낮은부적합율은엽채류에비해질량대비표면적이작기때문이고또한작물의생육에따른희석효과를고추로비교한보고와도유사한다 11). 전년도와같이 procymidone(17.1%), endosulfan(14.8%) 과 chlorfenapyr(11.4%) 이검출빈도가높음을알수있다. Procymidone, endosulfan과 chlorfenapyr 등은유기염소계

7 Survey on Pesticide Residues in Commercial Agricultural Products in the Northern Area of Seoul 33 Table 5. Frequency of detected and violated pesticides by year Pesticide ) ) ) * 서울시보건환경연구원보 Azoxystrobin 1(0.5) Bifenthrin 9(1.7) 5(1.5) 1(1.4) 1(0.5) Bitertanol 1(0.2) Cadusafos 2(0.4) 2(2.9) 1(0.3) 1(1.4) 1(0.5) 1(1.9) Captan 2(0.6) Carbofuran 1(0.5) 1(1.9) Chlorfenapyr 30(5.5) 15(4.5) 2(2.9) 7(3.6) 1(1.9) Chlorothalonil 7(0.2) 1(1.4) 3(1.5) Chlorpyrifos 14(2.6) 5(7.2) 8(2.4) 4(5.7) 14(7.1) 5(9.4) Chlorpyrifosmethyl 1(0.2) 1(1.4) 1(0.5) Cycloprothrin 1(0.2) Cypermethrin 3(0.6) 1(0.3) 1(0.5) Cyprodinil 1(0.2) 3(0.9) 1(0.5) Diazinon 11(2.0) 2(2.9) 9(2.7) 4(5.7) 5(2.5) 3(5.7) Dichlofluanid 1(0.2) 5(1.5) Dichlorvos 1(0.3) Diethofencarb 33(6.1) 1(1.4) 20(6.0) 3(4.3) 5(2.5) Dimetomorph 2(0.4) 2(2.9) 1(0.3) Endosulfan 160(29.6) 8(11.6) 67(19.9) 8(11.4) 25(12.7) 4(7.5) EPN 1(0.2) 1(1.4) 1(0.5) 1(1.9) Ethoprophos 4(0.7) 4(5.8) 6(1.8) 5(7.1) 5(2.5) 4(7.5) Fenarimol 1(0.2) 1(1.4) 4(1.2) 2(2.9) 2(1.0) 2(3.8) Fenitrothion 1(0.2) 1(1.4) 2(0.6) 1(1.4) 2(1.0) 2(3.8) Fenobucarb 2(0.4) 1(0.3) Fenpropathrin 2(0.4) 2(2.9) Fenthion 1(0.2) 1(0.3) 2(1.0) 2(3.8) Fenvalerate 1(0.5) Fipronil 2(1.0) 2(3.8) Fluazifop-buthyl 1(0.2) Fludioxonil 2(0.4) 1(1.4) 1(0.3) Flutoranil 3(0.6) 2(0.6) 1(1.4) Fosthiazate 1(0.2) 1(1.4) Hexaconazole 5(0.9) 3(4.3) 1(0.3) 1(1.4) Imazalil 1(0.2) 1(0.3) Iprobenfos 8(1.5) 1(0.3) 1(1.4) 6(3.0) 1(1.9) Iprodione 1(0.5) 1(1.9) Isoprothiolane 5(0.9) 3(4.3) 5(1.5) 4(5.7) Krexosim-methyl 11(2.1) 8(11.6) Mepanipyrim 4(0.7) 4(5.8) 3(0.9) 2(2.9) 1(0.5) 1(1.9) Metalaxyl 32(6.0) 5(7.2) 20(6.0) 7(10.0) 7(3.6) Methamidophos 1(0.2)

8 34 Sung-kyu Park et al. Myclobutanil 3(0.9) Oxadiazon 1(0.2) Oxadixyl 1(0.2) Parathion 1(0.2) 1(1.4) 1(0.3) 1(1.4) Penconazole 1(0.5) 1(1.9) Pencycuron 5(0.9) 5(7.2) 3(0.9) 3(4.3) Pendimethalin 1(0.2) 2(0.6) 1(1.4) 3(1.5) 1(1.9) Phenthoate 2(0.4) 2(0.6) 1(1.4) 1(0.5) Phorate 1(0.5) Pirimiphos-methyl 4(1.2) 1(1.4) Posphamidon 1(0.2) 1(1.4) Procymidone 139(25.7) 4(5.8) 109(32.4) 12(17.1) 69(35.0) 13(24.5) Propamocarb 2(0.4) 1(1.4) 2(0.6) 1(1.4) 2(1.0) 2(3.8) Prothiofos 1(0.5) 1(1.9) Pyridaben 1(0.2) 1(0.3) Pyrimethanil 1(0.3) Tebuconazole 4(0.7) 1(0.3) 1(1.4) 1(0.5) 1(1.9) Tebufenpyrad 5(0.9) 1(0.3) 6(3.0) Terbufos 1(0.2) 1(0.3) Tetradifon 3(0.9) 1(1.4) 3(1.5) 1(1.9) Tolclofos-methyl 1(0.3) Tolyfluanid 1(0.2) 1(0.3) Triadimefon 3(0.6) Triadimenol 2(0.6) Triflumizole 1(0.2) 1(1.4) 2(0.6) 1(1.4) 1(0.5) 1(1.9) Vinclozolin 8(1.5) 10(3.0) 12(6.1) 1(1.9) Zoxamide 1(0.2) ) ) Pesticide Azoxystrobin 8(1.5) 19(19.2) 6(1.1) 2(3.5) Benfuracarb 1(0.2) BHC 1(0.2) Bifenthrin 39(7.5) 2(2.0) 10(1.8) 3(0.6) Boscalid 1(0.2) 1(1.0) Bitertanol 2(0.4) 1(0.2) Buprofezin 7(1.3) 4(0.8) Carbaryl 1(0.2) Carbendazim 6(6.1) 2(0.3) 2(3.5) Cadusafos 1(0.2) 1(0.2) 1(1.7) Captan 1(0.2) Chlorfenapyr 66(12.7) 2(2.0) 86(14.4) 4(6.9) 54(10.1) 1(1.3) Chlorfluazuron 1(0.2) Chlorothalonil 22(4.2) 5(5.1) 20(3.4) 1(1.7) 22(4.1) 3(4.0) Chlorpyrifos 6(6.1) 18(3.0) 1(1.7) 15(2.8) 4(5.3) Chlorpyrifosmethyl 1(1.0) 1(0.2) 1(1.3) Cycloprothrin 1(1.0) 1(0.2) Cyhalothrin 3(0.5) Cypermethrin 32(6.2) 16(2.7) 23(4.3) Cyprodinil 2(0.3) 1(0.2)

9 Survey on Pesticide Residues in Commercial Agricultural Products in the Northern Area of Seoul 35 Diazinon Diazinon 10(1.9) 6(6.1) 6(6.1) 13(2.2) 13(2.2) 16(3.0) 16(3.0) 10(13.3) 10(13.3) Dichlorvos 11(1.8) 1(1.7) 2(2.7) Diethofencarb 10(1.9) 3(0.0) 3(0.5) 2(3.5) 14(2.6) 1(1.3) Dimetomorph 13(2.5) 14(14.1) 4(0.8) Diniconazole 4(0.8) 2(2..0) 78(13.1) 11(19.0) 6(8.0) Endosulfan 79(15.2) 9(9.1) 4(0.8) 2(3.5) 121(22.7) 1(1.3) EPN 1(0.2) Ethaboxam 2(2.0) 8(1.3) 3(5.2) 4(5.3) Ethoprophos 1(0.2) 3(3.0) 1(0.2) 7(1.3) Fenamidone 1(0.2) Fenarimol 1(0.2) 1(0.2) Fenitrothion 1(0.2) 1(1.3) Fenobucarb 1(0.2) 1(0.2) Fenpropathrin 2(0.4) 1(1.0) Fenthion 10(1.8) Fenvalerate 5(1.0) 2(0.2) 4(0.8) Fluacrypyrim 1(0.2) Fluazifop-buthyl 2(0.3) 1(1.7) 2(2.7) Fludioxonil 1(0.2) 4(4.0) 1(0.2) 9(1.7) Flufenoxuron 2(0.4) Fluquinconazole 1(1.0) 6(1.1) 1(1.7) Flutoranil 4(0.8) 9(9.1) 1(0.2) Fosthiazate 10(1.8) 1(1.7) Hexaconazole 6(1.2) 5(0.9) 3(4.3) 7(1.3) Imazalil 2(0.3) 2(0.4) Iprobenfos 1(0.2) 1(0.0) 3(0.5) 2(0.4) 3(4.0) Iprodione 2(0.2) 1(1.3) Iprovalicarb 1(0.2) Isoprothiolane 3(0.5) 5(0.9) 3(4.0) Lufenuron 1(0.1) Kresoxim-methyl 1(0.2) 4(0.4) 7(1.3) 1(0.2) 8(1.5) 7(9.3) Mepanipyrim 1(0.2) 1(1.3) Metalaxyl 27(5.2) 3(0.0) 6(1.1) 2(3.5) 23(4.2) 5(6.7) Methidahthion 1(0.2) 3(0.5) 1(1.7) methomyl 1(0.2) Methoxyfenazide 2(0.4) Oxadixyl 1(0.2) 1(1.7) Paclobutrazole 1(0.1) Parathion 1(0.2) 1(0.2) 3(0.6) 2(2.7) Pencycuron 1(0.2) 4(0.0) Pendimethalin 1(0.2) 2(0.3) 6(1.1) Penpropahtrin 2(0.3) Permethrin 1(0.2) Phenthoate 1(0.2) 5(0.8) 2(3.5) Phosphamidone 1(0.2) 1(1.3) Procymidone 119(22.9) 8(0.0) 184(30.8) 8(13.8) 147(27.6) 9(12.0) Prothiofos 2(0.3) Propamocarb 1(0.0) 4(0.8) 2(3.5) 1(0.2) 1(1.3) Pyridaben 2(0.4) 8(1.3) 1(1.7) 2(0.4) Pyridaryl 3(0.3) Pyrimethanil 3(0.6) 1(0.2) Pyraclofos 1(0.2) Simazine 2(0.3) spiromecifen 4(0.4) Tebuconazole 8(1.5) 1(0.0) 6(1.1) 1(1.7) 10(1.9) Tebupyrimfos 1(0.1) 1(0.2) 1(1.7) Tebufenpyrad 2(0.4) 2(0.3)

36 Sung-kyu Park et al. Terbufos 2(0.4) 1(0.2) Tetraconazole 11(2.1) 2(0.2) 10(1.8) 2(3.5) Tetradifon 1(0.2) 1(0.2) Thiamethoxam 1(0.2) 2(0.2) Thiopanate-methyl 4(0.8) 1(0.2) 1(1.7) Tolyfluanid 3(0.

Table 6. Detection and violation rates of pesticides in agricultural products by year. Fig. 3. Violation rates of pesticides in agricultural products by year.

10 36 Sung-kyu Park et al. Terbufos 2(0.4) 1(0.2) Tetraconazole 11(2.1) 2(0.2) 10(1.8) 2(3.5) Tetradifon 1(0.2) 1(0.2) Thiamethoxam 1(0.2) 2(0.2) Thiopanate-methyl 4(0.8) 1(0.2) 1(1.7) Tolyfluanid 3(0.6) 7(1.2) 3(0.6) Triflumizole 2(0.3) 1(1.7) 3(0.6) 1(1.3) Vinclozolin 6(1.2) 1(1.0) 8(1.3) 1(1.7) 6(1.1) 1(1.3) * Figures in parenthesis represent percent Fig. 2. Pesticides exceeded their MRLs in agricultural products. Table 6. Detection and violation rates of pesticides in agricultural products by year. Fig. 3. Violation rates of pesticides in agricultural products by year. 로잔류위험성은적고신생아에게상대적으로위험성이높다고알려져있으나, 살충제로써의그사용은점차늘고있다. Procymidone은 30년전부터사용하기시작한농약으로식물체내침투력이강하고효과가지속적이며내우성을지닌특성을가지고있으나 2006년도에비하여 40% 정도의사용감소를보이고있는데, 그이유는대체농약의개발과합계농약기준의강화 10) 와도연관이있는것으로판단된다. 결론 2007 년 1 월부터 12 월까지서울강북지역 ( 백화점, 대형할 Total No. of samples analyzed Sample detected with pesticide Sample exceeded MRL Year No. % No. % 인점, 재래시장 ) 에서유통되고있는엽채류, 과채류, 엽경채류, 과실류등농산물 145종 3,020건을다종다성분농약동시시험법에따라시료를전처리후 GC-ECD, GC-NPD, GC-FPD를이용하여 198종농약성분을, HPLC-FLD, HPLC-UVD를이용하여 62종농약을분석하였으며, 검출된농약성분의정성확인에는 GC-MSD(Hewlett Packard , USA), LC-MSD SL(Agilent, USA) 를사용하였고결과는다음과같다. 1. 농산물 3,020건중 145종 616건에서농약성분이검출되어 20.4% 의검출율을보였으며, 잔류농약검출율중 Procymidone이 105건 (17.1%) 으로가장많이검출되었으며

11 Survey on Pesticide Residues in Commercial Agricultural Products in the Northern Area of Seoul 37 검사건수대비검출율이높은농산물은엽채류 (11.3%), 과채류 (4.4%), 엽경채류 (2.0%), 장과류 (0.5%), 차류 (0.5%), 감귤류 (0.5%), 콩류 (0.4%), 근채류 (0.3%) 순이었다. 2. 잔류기준을초과한농산물은 64종 124건으로시금치 17건 (0.56%), 깻잎 14건 (0.46%), 얼갈이 11건 (0.36%), 쑥갓 10건 (0.33%), 취나물 10건 (0.33%), 부추 10건 (0.33%), 근대 9건 (0.30%) 순으로나타났다. 3. 농약잔류기준을초과한농약은 procymidone 105건 (17.1%), endosulfan 91건 (14.8%), chlorfenapyr 70건 (11.4%), bifenthrin 44건 (11.1%), cypermethrin 36건 (1.2%), metalaxyl 34건 (5.5%), chlorothalonil 27건 (4.4%), azoxystrobin 27건 (4.4%) 등이높은비중으로검출되었다. 4. 농약잔류허용기준을초과한농약성분은 39종으로 azoxystrobin 18회 (13.0%), dimethomorph 15회 (10.8%), endosulfan 9회 (6.5%), flutolanil 9회 (6.5%), procymidone 8 회 (13.8%), diazinon 6회 (5.8%), pencycuron 5회 (3.6%) 로가장높은빈도수로나타났으며, 특히 spiromecifen은 4회 (2.9%) 로처음검출되는농약으로최다빈도를기록하였으며, Fenpropathrin, Lufenuron, Paclobutrazole, Pencycuron, Thiamethoxam도 2007년에처음으로기준이초과되어검출되었다. 참고문헌 1. Takayuki Shibamoto : Resticide regulation and Residue monitoring in the United State of America. 食衛誌, , (2002). 2. 정영호, 김장억, 김정한, 이영득, 임치환, 허장현 : 최신농약학, 시그마프레스, 서울, pp.22~23 (2000). 3. 심이성, 김진원 : 농약학, 월드사이언스, 서울, pp.8 (2005). 4. U.S. Food and Drug Administration: Food and Drug Administration Pesticide Program, Residue Monitoring, (2001). 5. European Commission: Monitoring of Pesticide Residues in Products of Plant Origin in the European Union, Norway, Iceland and Liechtenstein 2001 Report, SANCO/20.03 final, (2003). 7. 후생노동성생활위생국식품화학과편 : 식품중잔류농약, 일본식품위생협회, (1999). 8. 식품의약품안전청 : 고시제 호 9. 박성규, 김복순, 신기영, 조태희, 김미선, 이재규, 이상미, 최성민, 강희곤 : 서울시보건환경연구원, 42:198~211,2006, 서울시강북지역유통농산물중의농약잔류실태조사 (2006). 10. 한국식품공업협회 : 식품공전, 문영사, (2006). 11. 식품의약품안전청 : 고시제 , 68 호. 12. 성기용, 최규일, 정몽희, 허장현, 김정규, 이규승 : 시설재배고추중 Bitertanol 및 Tebuconazole 잔류양상. 한국농화학회지, 47, ,(2004)

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-041Æ¯Áý3c00Ì¹Ì°æš Research Trends on the Development of Scientific Evidence on the domestic Maximum Residue Limits of Pesticides Mi-Gyung Lee *, Jae-Han Shim 1, Sanghoon Ko 2, Hae-Rang Chung 3 *, 1, 2, 3 Department of Food