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1 pissn J. Fd Hyg. Safety Vol. 29, No. 3, pp. 170~180 (2014) Journal of Food Hygiene and Safety Available online at 년서울북부지역유통농산물의잔류농약모니터링및위해성평가 김남훈 * 이정숙 김욱희 최영희 한성희 김윤희 김희선 이새람 이정미 유인실 정권 서울특별시보건환경연구원강북농수산물검사소 Monitoring of Pesticide Residues and Risk Assessment on Agricultural Products Marketed in the Northern Area of Seoul in 2013 Nam Hoon Kim*, Jeong Sook Lee, Ouk Hee Kim, Young Hee Choi, Sung Hee Han, Yun Hee Kim, Hee Sun Kim, Sae Ram Lee, Jeong Mi Lee, In Sil Yu, and Kwon Jung Kangbuk Agro-Fishery Products Inspection Center, Seoul Metropolitan Government Research Institute of Public Health and Environment, , Korea (Received May 28, 2014/Revised June 10, 2014/Accepted August 20, 2014) ABSTRACT - The aim of this study was to investigate pesticide residues in 2,877 market vegetables in the northern area of Seoul in Pesticide residues in the samples were analysed by multiresidue method for 285 pesticides using GC-ECD/NPD and HPLC-DAD/FLD. 385 samples(13.4%) were detected with pesticide residues at or below MRL, and 15 samples(0.5%) were found to detect pesticide residues exceeding MRL. The most frequently detected samples were sedum(63.6%), chamnamul(45.8%), leek(44.5%) and green&red pepper(30.8%). Among the 15 violated samples, leek(5 cases) and welsh onion(4 cases) showed the highest violation rate. A total of 74 samples(18.5%) contained multiple pesticide residues in one vegetable. Procymidone, chlorofenapyr and cypermethrin were the pesticide most frequently found. As a tool of risk assessment through the consumption of pesticide detectable agricultural products, the ratio of estimated daily intake (EDI) to acceptable daily intake (ADI) was calculated into the range of 1.05~28.61%. The results have meant that there was no health risk through dieting commercial agricultural products detected with pesticide residues. Key words : pesticide residues, agricultural products, risk assessment, %ADI 농약은병해충으로부터농작물을보호하고농산물의품질과생산량을증가시키기위하여폭넓게사용되고있으며노동력절감을위한필수불가결한농자재라는유익성을가지는반면때로는인간과환경에위해성을끼치는양면성을가지고있다 1,2). 농업분야에서농약사용은 2차세계대전이후로농산물의생산성을높이기위하여사용량이급격히증가하였으며이로인해식품등의농산물뿐만아니라토양, 강등의주위환경에농약성분과그대사산물이잔류함에따라건강상의위해를끼치는요인이되었다 3). 현재 1000여종류이상의화합물이곰팡이, 해충및잡초제거를위해농약으로사용되고있는실정이며이러한농약성분들이오남용으로농산물에부적절하게사 *Correspondence to: Namhoon Kim, Seoul Metropolitan Government Research Institute of Public Health and Environment, Jegi-dong, Dongdaemun-gu, Seoul, Korea Tel: , Fax: nhkim70@seoul.go.kr 용되었을경우그독성으로인해인간의건강을위협하는위해요인으로인식되고있으며단기노출시에는두통, 구토등을유발하고장기간노출시에는암발생, 생식계이상및내분비계질환과관련되어있는것으로보고되고있다 4,5). 세계보건기구 (WHO) 에의하면매년전세계적으로 300만건이상의농약중독사고가발생하며이중약 22만명이사망하는것으로보고되었다 6). 하지만최근에는환경피해방지등독성문제에대한인식증가와소비자의식품안전에대한관심증대및친환경농업증가로인해농약사용이점차감소하고있는추세이다. 한편, 농약의오남용을방지하고국민건강에피해를주지않도록각농약별사용량, 사용횟수, 수확기에따른살포횟수및시기등에관한농약안전사용기준과농약의최대잔류허용기준을설정하여사용방법과사용량을엄격히규제하고있다 7). 잔류농약이란식품에농약의잔류가일정농도남아있는것을말하며농약잔류허용기준 (Maximum Residue Limit, MRL) 은식품을섭취하는소비자의안전을위하여유통되 170

2 Monitoring of Pesticide Residues and Risk Assessment on Agricultural Products Marketed in the Northern Area of Seoul in 는농산물에잔류할수있는농약의양을법으로정한것이다. 또한이는농작물재배시농약이적절히사용되는지여부를확인할수있는이중역할을하고있다 8). 농산물의생산량증대및우수한상품성유지를위하여사용되는농약으로부터발생할수있는식품안전사고를예방함과동시에농업환경변화에따른신속한대응방안을마련하기위하여각나라마다식품중의농약잔류허용기준을설정하여관리하고있다 9). 농약의안전관리기준은식품의섭취량에대한식품별농약잔류허용기준치간의계산을통하여할수있는데, 식품중의이론적최대농약잔류허용치는사람이식품을통해섭취하는농약의 1일섭취허용량 (Acceptable daily intake, ADI) 으로제안된다. 일반적으로농약 1일섭취허용량의 80% 에해당하는양에국민의평균체중을곱하여 1인당 1일섭취량으로나누어식품중의이론적최대농약잔류허용치를산출할수있다 10). 우리나라의경우식품의약품안전처에서 1988년 28종농산물 17종농약에대한농약잔류허용기준을설정한이래 2013년고시개정을통해 439종으로확대된농약에대한기준을설정하여관리하고있다 11). 미국의경우는농약의등록과잔류허용기준설정및위해성평가업무는환경보호청 (Environmental Protection Agency, EPA) 이관장하고있으며연방농약법 (Federal Insecticide, Fungicide and Rodenticide, FIFRA) 으로규정하여현재 380종의농약에대하여잔류허용기준이설정되어있다 12). 이처럼세계각국은농산물및식품에대한잔류농약의안전성을평가하기위하여잔류허용기준을설정하여규제할뿐만아니라자국및수입농산물중잔류농약을분석하고그실태를조사하고있다 13). 이러한잔류농약모니터링결과를바탕으로한위해성평가는 1990년대이후우리나라에서본격적으로연구되기시작하였으며그후이론적식이섭취량에따른농약잔류허용기준의타당성및섭취량산출방법에대한연구와더불어 1일추정섭취량에따른농산물섭취에의한위해성평가연구가국내외적으로많이보고되고있는실정이다 2,7-8, ). 따라서본연구에서는 2013년서울북부 ( 강북 ) 지역대형마트등에서유통되는농산물을대상으로잔류농약모니터링을실시하였으며그결과를토대로각농산물에서검출된농약에대한섭취량을추정하여위해성을평가하고자하였다. 통되고있는일반농산물및친환경 ( 무농약포함 ) 농산물 127품목 2,877건을대상으로잔류농약을검사하였으며분석대상농약은 Table 1과같이 285종을대상으로하였다. 시약및기구모든분석대상농약의표준물질은 Dr Ehrensforfer GmbH (Augsburg, Germany), Chem Service사 (West Chester, USA), Sigma-Aldrich (St. Louis, USA), Honeywell사 (Wunstorfer, Germany) 의제품을사용하였다. 사용된모든표준물질의순도는싸이퍼메쓰린 ( 순도 91.5%) 을제외한모든제품이 98% 이상이었다. 농약추출을위한용매로서아세토니트릴은 JT & Baker (Center Valley, USA) 의제품을사용하였으며정제에사용된아세톤과헥산은 Kanto Chemical (Tokyo, Japan) 의제품을사용하였다. 층분리를위해사용한염화나트륨 (Sodium Chloride) 은 Merck (Darmstadt, Germany) 제품이었다. 시료분쇄를위한분쇄기로는 Robot Coupe사의 Blixer 5 plus (Vincennes, France) 를이용하였다. 정제용고체상추출 (SPE) 카트리지는 Agilent Technologies의용량 1 GM (6 cc) 의 Florisil 카트리지 (Santa Clara, USA) 를사용하였으며 Sigma-Aldrich의 SUPELCO VISIPREP TM vacuum manifold (St. Louis, USA) 를이용하여동시에여러시료를정제하였다. 농약추출분쇄장치인 Homogenizer는 Omin 사의 Omni Macro Homogenizer (Kennesaw, USA) 를이용하였으며시료농축을위한질소농축기는 Organomation Associates, Inc. 의 N-EVAP TM 112 (Berlin, USA) 을사용하였다. 기기및분석방법시료전처리및분석은식품공전의식품중잔류농약분석법의다종농약다성분분석법제 2법에따라실험하였다 11). 분석에사용된 GC는 Agilent Technologies (Santa Clara, USA) 의 HP 6890 및 7890제품으로유기염소계농약은전자포획 (µecd) 검출기를연결하여사용하였고유기인계농약은질소인 (NPD) 검출기로분석하였다. 농약검출확인을위한질량 (MSD) 검출기는 HP 5973 모델을사용하였다. HPLC-DAD는 Agilent 1100 series를, HPLC- FLD는 Waters사 (Milford. USA) 의 2695 모델을사용하여분석하였다. 분석에사용된컬럼및기기분석조건은 Table 2-4와같다. 재료및방법 실험대상농산물및분석농약 2013년 1월부터 12월까지서울북부 ( 강북, 광진, 노원, 도봉, 동대문, 마포, 서대문, 성동, 성북, 용산, 은평, 종로, 중구, 중랑 ) 지역백화점, 대형매장및재래시장등에서유 잔류농약의위해성평가검출된개별농약의위해성평가는농약이검출된농산물을섭취할경우를가정하여농산물중검출농약의평균잔류량 (mg/kg) 을농산물의 1일섭취량 (kg/day) 과곱하여잔류농약 1일섭취추정량 (Estimated daily intake, EDI, mg/ kg bw/day) 을산출하였다. 잔류농약 1일섭취허용량

3 172 Nam Hoon Kim et al. Table 1. List of target pesticides monitored in this survey Classification Insecticide (136) Herbicide (57) Fungicide (87) Plant growth regulator (5) Pesticide Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldrin, Azinphos-Methyl, Benfuracarb, Benzoximate, BHC, Bifenthrin, Bromopropylate, Buprofezin, Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Carboxin, Chlorantraniliprole, Chlordane, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlorobenzilate, Chlorpyrifos, Chlorpyrifos-methyl, Chromafenozide, Clothianidin, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin, DDT, Deltamethrin, Diazinon, Dichlorvos, Dicofol, Dieldrin, Diflubenzuron, Dimethoate, Dimethylvinphos, Disulfoton, Endosulfan, Endrin, EPN, Esprocarb, Ethiofencarb, Ethion, Ethoprophos, Etoxazole, Etrimfos, Fenamiphos, Fenazaquin, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyroxymate, Fensulfothion, Fenthion, Fenvalerate, Fipronil, Flonicamid, Fluacrypyrim, Flubendiamide, Flucythrinate, Flufenoxuron, Fluvalinate, Formothion, Fosthiazate, Heptachlor, Hexaflumuron, Imidacloprid, Indoxacarb, Isazofos, Isofenphos, Isoprocarb, Lufenuron, Malathion, Mecarbam, Metaflumizone, Metamidophos, Methidathion, Methiocarb, Methomyl, Methoxychlor, Methoxyfenozide, Metolcarb, Mevinphos, Monocrotophos, Novaluron, Omethoate, Oxamyl, Parathion, Parathion-Methyl, Permethrin, Phenothrin, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidone, Phoxim, Pirimicarb, Pirimiphos-ethyl, Pirimphos-methyl, Profenofos, Propoxur, Prothiofos, Pymetrozine, Pyaclofos, Pyrethrines, Pyridaben, Pyridaryl, Pyridaphenthion, Pyrimidifen, Pyriproxyfen, Quinalphos, Simeconazole, Spirodiclofen, Spiromecifen, Tebufenozide, Tebefenpyrad, Tebupirimfos, Telfubenzuron, Tefluthrin, Thiacloprid, Thiamethoxam, Thiodicarb, Thiometon, Tralomethrin, Triazmate, Triaophos, Vamidothion Acetochlor, Alachlor, Anilofos, Bendiocarb, Bifenox, Bromacil, Bromobutide, Butachlor, Cinosulfuron, Cyhalofop-butyl, Dichlobenil, Diclofop-methyl, Dimepiperate, Dimethenamid, Diphenaimd, Dithiopyr, Diuron, Ethalfluralin, Fluazifop-butyl, Flufenacet, Flumioxazine, Indanofan, Linuron, Mefenacet, Metamifop, Methabenzthiazuron, Metobromuron, Metolachlor, Metribuzin, Molinate, Napropamide, Norflurazon, Oryzalin, Oxadiazon, Oxaziclomefone, Oxyfluorfen, Pendimethalin, Pentoxazone, Pretilachlor, Piperophos, Prometryne, Propanil, Propisochlor, Pyrazolate, Pyribenzoxim, Pyributicarb, Pyriminobac-methyl, Quinoclamine, Simazine, Simetryn, Tebutryne, Tebuthylazine, Thenylchlor, Thiazopyr, Thiobencarb, Tri-allate, Trifluralin Amisulbrom, Azoxystrobin, Benomyl, Benthiavalicarb-isopropyl, Bitertanol, Boscalid, Captapol, Captan, Carbendazim, Chinomethionat, Chlorothalonil, Cyazofamid, Cyflufenamid, Cymoxanil, Cyproconazole, Cyprodinil, Dichlofluanid, Dicloran, Diethofencarb, Dimetomorph, Diniconazole, Diphenylamine, Edifenphos, Ethaboxam, Fenamidone, Fenarimol, Fenobuconazole, Fenhexamid, Fenoxanil, Ferimzone, Fluazinam, Fludioxonil, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Folpet, Fthalide, Furathiocarb, Imazalil, Imibenconazole, Iprobenfos, Iprodione, Iprovalicarb, Isoprothiolane, Kresoxim-methyl, Mepanipyrim, Mepronil, Metalaxyl, Metconazole, Metrafenone, Myclobutanil, NItrapyrin, Nuarimol, Oxadixyl, Ofurace, Penconazole, Pencycuron, Probenazole, Prochloraz, Procymidoen, Propamocarb, Propiconazole, Pyaclostrobin, Pyrazophos, Pyrimethanil, Pyroquilon, Quintozene, Tebuconazole, Tecnazene, Tebusof, Tetraconazole, Tetradifon, Thifluzamide, Thiophanate-methyl, Tiadinil, Tolclofos-methyl, Tolyfoluanid, Triadimefon, Triadimenol, Trichlorfon, Tricylazole, Trifloxystrobin, Triflumizole, Triflumuron, Vinclozolin, Zoxamide Chlorpropham, Forchlorfenuron, Hexaconazole, Paclobutrazole, Uniconazole Table 2. Analytical conditions used for gas chromatography Specification GC-µECD GC-NPD Column Temp. Front Back Oven DB % cyanopropyl phenyl methyl (30 m 320 µm ID 0.25 µm) HP-5 5% phenyl methyl siloxane (30 m 320 µm ID 0.25 µm) 150 o C (1min) 12 o C/min 240 o C (2min) 10 o C/min 280 o C (11 min) 110 o C (2min) 15 o C/min 200 o C (8min) 10 o C/min 260 o C (7 min) Injection 230 o C 210 o C Detector 280 o C 270 o C Gas flow N 2 (1.0 ml/min) N 2 (1.4 ml/min) Air (60.0 ml/min) H 2 (3.5 ml/min) (Acceptable daily intake, ADI, mg/kg bw/day) 은식품의약품안전처잔류농약데이터베이스에서제공하는값을이용하였으며 19) 이두값을비교하여위해성을평가하고자하였 다. 개별농산물의식이섭취량은 2011년국민건강통계국민건강영양조사 5기 2차년도자료를참고하였다 20). 개별농약의 ADI에각각한국성인의평균체중 64.8(kg bw) 21)

4 Monitoring of Pesticide Residues and Risk Assessment on Agricultural Products Marketed in the Northern Area of Seoul in Table 3. Analytical conditions used for GC-MSD Specification GC-MSD Column HP-5MS 5% phenyl methyl siloxane (30 m 250 µm ID 0.25 µm film thickness) Temp. Oven 100 o C (2 min) 10 o C/min 280 o C (15 min) 10 o C/min 280 o C (11 min) Injection 230 o C Carrier gas He (splitless, 1.0 ml/min) MSD parameter Ionization method Electron impact at 70 ev Ion source temp. 230 o C Transfer line temp. 280 o C Scan range m/z (2.91 scan/sec) Table 4. Analytical conditions used for HPLC-DAD and HPLC-FLD Specification HPLC-FLD HPLC-DAD Detector Scanning fluorescence detector Diode array and multiple wavelength detector Column Waters carbamate analysis column ( mm) Zobax Eclipse XDB-C18 (5.0 µm, mm) Wavelength Ex λ: 339 nm, Em λ:445 nm 200 nm, 254 nm Flow rate 0.9 ml/min 1.0 ml/min Injection vol. 10 µl 10µl Mobile phase A: 12% MeOHB : MeOH : AcCN : Water (35: 35: 30) A: 100 % Acetonitrile B: Water Time (min) A (%) B (%) Time (min) A (%) B (%) Gradientprogram 을곱하여한국인의 1인1일최대섭취허용량 (maximum permissible intake, MPI, mg/day/person) 을구하였다. 그리고잔류농약섭취허용량대비식이섭취율 %ADI와 %MPI 를계산하였다. 결과및고찰 농산물별잔류농약검출및부적합현황 2013년서울강북지역에서유통된농산물 2,877건 ( 채소류 2,488건, 과일류 244건, 두채류 58건, 버섯류 33건, 서류 33건, 견과종실류 9건, 곡류 11건, 콩류 1건 ) 에대하여동시분석이가능한 285종에대한잔류농약실태를조사한결과 Table 5와같았다. 전체농산물중잔류허용기준 (Maximum Residue Level, MRL) 이하로농약이검출된농산물은 385건으로 13.4% 의검출률을보였으며, 농약잔류허용기준을초과한농산물은 15건으로전체농산물중 0.5% 를차지하였다. 이를지난 5년간강북지역유통농산물에대한잔류농약모니터링결과와비교해보면검출률과부적합률모두 5년전에비해감소하였음을알수있다. Kim 등 22) 의보고에따르면검출률은 2009년 25.6%, 2010년 15.1%, 2011년 14.8%, 2012년 12.9% 이었으며부적합률은 2009년 2.2%, 2010년 0.7%, 2011년 1.0%, 2012년 0.9% 로서 2009년에비해 2배이상감소하였음을확인할수있었다. 이는농약검사위생기관의지속적인모니터링감시효과와더불어재배농가또한친환경농사의비중을확대함에따른결과에기인한것으로판단된다. 외국의결과와비교해보면 Jardim 등 23) 이브라질내생산된농산물 13,556건을대상으로 2001년부터 2010년까지잔류농약모니터링결과검출률은 48.3%, 부적합률은 3% 라고보고하였다. 이는본실험의결과와는상당한차이가있는것으로농약사용량은국가마다다르며기후등재배지역의특성및재배농산물에따라큰차이가있을것으로생각된다. 농약검출률을감소시키기위해서는규제당국의농약잔류량최소를위한노력이필요하며이를위해재배농민들에대하여적절한농약사용법및사용량에대한교육등이수반되어야한다. 농산물분류에따른잔류농약분포를살펴보면채소류는전체 2,488건중 356건 (14.3%) 에서잔류농약이검출되었으며과일류는 11.1%, 서류는 6.1% 검출되었다. 반면에버섯류, 견과종실류, 곡류, 콩류및두채류는잔류농약이

5 174 Nam Hoon Kim et al. Table 5. Results of pesticide residues detected below and over MRL in agricultural products Type Group Commodity samples analyzed No. of sample detected (%) No. of sample violated (%) Vegetables Leafy vegetables Stalk andstem vegetables Root and tuber vegetables Fruiting vegetables, cucurbits Fruiting vegetables other than cucurbits Lettuce (leaf) (7.7) 1 (0.6) Spinach (14.2) 0 (0.0) Brassica leafy vegetables (14.0) 1 (0.9) Perilla leaves (25.0) 1 (1.0) Lettuce (head) 69 5 (7.2) 0 (0.0) Radish leaves 66 4 (6.1) 1 (1.5) Crown daisy 56 4 (7.1) 0 (0.0) Chicory 53 4 (7.5) 0 (0.0) Kale 38 1 (2.6) 0 (0.0) Mustard green 33 3 (9.1) 0 (0.0) Chamnamul (45.8) 0 (0.0) Chard 23 2 (8.7) 1 (4.3) Marsh mallow 22 2 (9.1) 0 (0.0) Chwinamul 21 5 (23.8) 0 (0.0) Mustard leaf 20 3 (15.0) 1 (5.0) Shepherd's purse 15 2 (13.3) 0 (0.0) Amaranth 10 3 (30.0) 0 (0.0) Pumpkin young leaves 10 2 (20.0) 0 (0.0) Others (5.1) 0 (0.0) Subtotal 1, (11.8) 6 (0.5) Welsh onion (21.5) 4 (2.1) Leek (44.5) 5 (3.2) Water dropwort 98 8 (8.2) 0 (0.0) Celery 60 9 (15.0) 0 (0.0) Green garlic 39 6 (15.4) 0 (0.0) Wild garlic 17 4 (23.5) 0 (0.0) Sedum 11 7 (63.6) 0 (0.0) Others 54 0 (0.0) 0 (0.0) Subtotal (23.4) 9 (1.5) Carrot 36 1 (2.8) 0 (0.0) Radish (root) 32 0 (0.0) 0 (0.0) Onion 32 0 (0.0) 0 (0.0) Garlic 16 0 (0.0) 0 (0.0) Others 47 0 (0.0) 0 (0.0) Subtotal (0.6) 0 (0.0) Cucumber (18.6) 0 (0.0) Squash 66 4 (6.1) 0 (0.0) Others 48 1 (2.1) 0 (0.0) Subtotal (10.5) 0 (0.0) Green & Red pepper (30.8) 0 (0.0) Sweet pepper (20.4) 0 (0.0) Eggplant 47 5 (10.6) 0 (0.0) Tomato 25 0 (0.0) 0 (0.0) Subtotal (21.4) 0 (0.0) Broccoli 66 0 (0.0) 0 (0.0) Flowerhead Korean cabbage 41 2 (4.9) 0 (0.0) brassicas Cabbage 11 0 (0.0) 0 (0.0) Subtotal (1.7) 0 (0.0) Subtotal 2, (14.3) 15 (0.6)

6 Monitoring of Pesticide Residues and Risk Assessment on Agricultural Products Marketed in the Northern Area of Seoul in Table 5. (Continued) Results of pesticide residues detected below and over MRL in agricultural products Type Group Commodity No. of sample No. of sample detected (%) No. of sample violated (%) Fruits Stone fruits Pome fruits Citrus fruits Jujube 12 2 (16.7) 0 (0.0) Peach 1 1 (100.0) 0 (0.0) Cherry 1 1 (100.0) 0 (0.0) Others 4 0 (0.0) 0 (0.0) Subtotal 18 4 (22.2) 0 (0.0) Apple 57 5 (8.8) 0 (0.0) Persimon 48 0 (0.0) 0 (0.0) Others 34 0 (0.0) 0 (0.0) Subtotal (3.6) 0 (0.0) Mandarin 26 7 (26.9) 0 (0.0) Orange 4 1 (25.0) 0 (0.0) Lime 1 1 (100.0) 0 (0.0) Others 3 0 (0.0) 0 (0.0) Subtotal 34 9 (26.5) 0 (0.0) Berries and other small fruits Assorted tropical and sub-tropical fruits Grape 19 4 (21.1) 0 (0.0) Strawberry 11 1 (9.1) 0 (0.0) Others 3 0 (0.0) 0 (0.0) Subtotal 33 5 (15.2) 0 (0.0) Kiwifruit 11 2 (18.2) 0 (0.0) Banana 5 1 (20.0) 0 (0.0) Mango 2 1 (50.0) 0 (0.0) Others 2 0 (0.0) 0 (0.0) Subtotal 20 4 (20.0) 0 (0.0) Subtotal (11.1) 0 (0.0) Mushrooms Oyster mushroom 8 0 (0.0) 0 (0.0) Others 25 0 (0.0) 0 (0.0) Subtotal 33 0 (0.0) 0 (0.0) Potatoes Potato 19 2 (10.5) 0 (0.0) Others 14 0 (0.0) 0 (0.0) Subtotal 33 2 (6.1) 0 (0.0) Nuts& seeds Peanut or nuts Chestnut 9 0 (0.0) 0 (0.0) Subtotal 9 0 (0.0) 0 (0.0) Cereal grains Rice 7 0 (0.0) 0 (0.0) Corn 4 0 (0.0) 0 (0.0) Subtotal 11 0 (0.0) 0 (0.0) Beans Sword jackbean 1 0 (0.0) 0 (0.0) Subtotal 1 0 (0.0) 0 (0.0) Sprout products Bean sprout 35 0 (0.0) 0 (0.0) Mung bean sprout 23 0 (0.0) 0 (0.0) Subtotal 58 0 (0.0) 0 (0.0) Total 2, (13.4) 15 (0.5) 검출되지않았다. 채소류중에서형태에따른검출률을살펴보면엽경채류 23.4%, 박과이외과채류 21.4% 및엽채류 11.8% 순으로검출률이높았다. 반면에근채류와결구엽채류는각각 0.6% 와 1.7% 의검출률을보여상대적으로매우낮았다. 채소류는곡류나과실류에비해제한된면 적에서집단화된시설재배가대부분이며이로인해병해충에취약하기때문에농약사용량이많으며이로인해잔류량또한높은것으로판단된다. 개별농산물중에서는돌나물 63.6%, 참나물 45.8%, 부추 44.5% 및고추 30.8% 순으로검출률이높았다. 이는 Kim 등 22) 의 2012년

7 176 Nam Hoon Kim et al. Table 6. Number of samples with multiple pesticide residues for one vegetable Vegetables No. of residues in one vegetable sample (%) Perilla leaves 5 (19.2) 2 (7.7) - 1 (3.8) 1 (3.8) Pepper leaves 1 (33.3) 2 (66.6) Lettuce (leafy) 1 (7.1) 2 (14.3) Leek 16 (21.6) 3 (4.1) Kiwifruit - 1 (50.0) Apple 1 (20.0) Brassica leafy vegetables 4 (23.5) Celery 2 (22.2) Chicory 1 (25.0) Cucumber 1 (6.3) Grape 1 (25.0) Green and red pepper 4 (11.1) Jujube 2 (100) Korean cabbage 1 (50.0) Lettuce (head) 1 (20.0) Mandarin 2 (28.6) Mustard green 2 (66.6) Red pepper (dried) 3 (60.0) Shepherd s purse 1 (50.0) Spinach 6 (25.0) Sweet pepper 1 (9.1) Welsh onion 5 (11.1) Total 61 (15.3) 10 (2.5) - 1 (0.3) 1 (0.3) 모니터링결과와약간의차이는있지만거의유사함을확인할수있었으며이를기초자료로사용하여차후잔류농약모니터링사업시검출률이높았던농산물을집중수거품목으로선정할필요성이있는것으로판단되었다. Table 6에서는하나의시료에서 2종이상의농약이동시에검출된결과를보여주며농약이검출된농산물 400 건중 74건 (18.5%) 의시료에서 2종이상의농약이검출되어적지않은농산물이 2종이상의농약에노출되어있음을확인할수있었다. 가장많은경우는 2종의농약이동시에검출된것으로모두 61건 (15.3%) 이었으며 3종의농약이동시에검출된경우는 10건 (2.5%) 이었다. 깻잎 1건에서는최대 6종의농약이동시에검출되기도하였는데 1 종의농약이인체에미치는위해성은이미알려진경우가많은것에비해다수의농약이혼합되어있을경우에는각농약성분간의상호작용을통해인체에미치는위해성정도를예측하기어려우며위해성평가연구또한미비한실정이다. 그러므로잔류농약기준적용시개별농약의잔류허용기준적용뿐만아니라검출농약의수와총량에따른기준적용도검토해봐야할것으로생각된다. 개별농 Table 7. Detailed results about pesticides exceeding MRL in various vegetables Vegetables Pesticides exceeding MRL Conc. of detection (mg/kg) MRLs (mg/kg) Leek Flutolanil Procymidone EPN Endosulfan Terbufos Welsh onion Dimethomorph Pyridalyl Iprodione Iprodione Lettuce (leaf) Procymidone Korean cabbage Diniconazole Perilla leaves Kresoxim-methyl Radish leaves Bifenthrin Chard Paclobutrazol Mustard leaf Diazinon 산물중에서는깻잎 9건 /26건(34.6%), 부추 19건 /74건 (25.7%), 시금치 6건 /24건(25%). 파 5건 /45건(11.1%) 순으로 2종이상의농약이검출된경우가많았으며이러한시민다소비농산물의섭취시더욱주의가필요할것으로판단되었다. 농산물잔류허용기준이상으로농약이검출된부적합농산물은부추 5건 (3.2%), 파 4건 (2.1%) 으로가장많았으며그외상추, 엇갈이배추, 깻잎, 무잎, 근대및갓에서 1건씩검출되어총 15건이었다. Table 7은부적합농산물과검출농약및검출량등을보여주며부적합농산물의잔류농약검출량은최소의경우상추에서프로시미돈이잔류허용기준의약 2배 (9.4/5.0 mg/kg) 의농도로검출되었으며부추에서는플루토라닐이기준치의최대 80배 (4.04/0.05 mg/ kg) 까지검출되기도하였다. 잔류허용기준이상으로검출된농산물들은모두엽채류와엽경채류로서실제섭취시세척및가열조리등에의해대부분의농약들이소실되기때문에안전한것으로알려지고있으며이밖에도소비자들이안전하게농산물을섭취할수있도록홍보및교육을강화할필요가있을것으로판단된다. 농약별잔류농약검출빈도 2013년잔류농약모니터링결과 285종의검사대상농약중정량한계이상으로검출된농약은아세타미프리드등 45종의농약이총 474회검출되었다 (Table 8). 이는 2012 년강북지역모니터링결과 52종의농약이 555회검출되었던것과비교하면약간감소한것으로확인되었다. 검출농약을생물학적작용 ( 용도 ) 에따른분류를하면살충제 22종이 217회 (45.8%), 살균제 21종이 254회 (53.6%), 제

8 Monitoring of Pesticide Residues and Risk Assessment on Agricultural Products Marketed in the Northern Area of Seoul in Table 8. Frequency of detectable pesticide residues found in the monitoring survey Classification by biological action Insecticide Pesticide Frequency of detection MRL a) > MRL b) Detection range (mg/kg) MRLs (mg/kg) Acetamiprid Bifenthrin ~ ~2.0 Chlorfenapyr ~ ~20.0 Chlorpyrifos ~ ~1.0 Cyhalothrin ~ ~2.0 Cypermethrin ~ ~5.0 Diazinon ~ Diniconazole ~ ~0.3 Endosulfan ~ ~0.1 EPN ~ Fenitrothion ~ ~2.0 Fenpropathrin ~ ~5.0 Fenpyroximate Fenvalerate ~ ~3.0 Flubendiamide ~ ~20.0 Malathion Methidathion Phenthoate ~ Pyridaben Pyridalyl ~ ~2.0 Tebufenpyrad ~ Terbufos ~ ~0.05 Subtotal Azoxystrobin ~ ~20.0 Boscalid ~ ~30.0 Captan Chlorothalonil ~ ~40.0 Cyprodinil Diethofencarb ~ ~30.0 Dimethomorph ~ ~20.0 Fenarimol Fludioxonil ~ ~7.0 Flutolanil ~ ~0.7 Fungicide Iprobenfos Iprodione ~ ~10.0 Isoprothiolane Kresoxim-methyl ~ ~2.0 Mepanipyrim Procymidone ~ ~7.0 Pyraclostrobin Pyrimethanil ~ ~10.0 Thifluzamide Tolyfluanid Triadimefon Subtotal Herbicide Pendimethalin Plantgrowth regulator Paclobutrazole ~ Total a) MRL: detectable pesticide residues below and at maximum residue limit. b) > MRL: detectable pesticide residues over maximum residue limit.

9 178 Nam Hoon Kim et al. 초제및생장조절제각 1종이 1회 (0.2%) 검출되어살균제가가장많이검출되는것으로파악되었다. 2011년도작물보호협회 24) 에서보고한국내에서출하된농약성분량조사에서는살충제 34.7%, 살균제 28.0%, 제초제 27.1% 및기타제 10.2% 로서살충제가가장많이국내에서생산된것으로보고되었다. 이를근거로유추해보면실제작물재배에살충제가살균제보다많이사용되기는하지만농작물잔류성이살균제가높아잔류농약모니터링검사에서가장빈번하게검출되는것으로판단되었다. 개별농약중에서가장빈번하게검출된농약은프로시미돈 160회 (0.013~ mg/kg), 클로르훼나피르 56회 (0.006~2.062 mg/kg), 싸이퍼메쓰린 44회 (0.024~1.533 mg/ kg), 클로로타로닐 25회 (0.011~3.687 mg/kg), 비펜스린 24 회 (0.012~0.657 mg/kg) 순이었다. 이는이전의모니터링결과와거의비슷하였으며검출빈도가높은농약들은매년비슷한양상으로검출되는것으로확인되었다. 2012년도에이어가장빈번하게검출되었던프로시미돈은물리화학적으로빛과열, 습기에안정한살균제로토양환경에서흡착량이높고살포된환경내에서분해가서서히진행되어약제의소실정도가느린특징이있는것으로알려지고있으며이런특성으로인해작물중잔류성이높고검출률이높게나오는것으로판단되었다. Han 등 25) 의 2011년잔류농약모니터링결과와 Kim 등 22) 의 2012년모니터링결과에서는엔도설판이각각 79회, 33회검출되어검출빈 Table 9. Commodities with pesticides from the same class in the monitoring survey Pesticide class No. of samples a) Vegetables (no. of samples) Pyrethroid 76 (16.0%) Organophosphate 29 (6.1%) Welsh onion(20), Spinach(15), Leek(9), Brassica leafy vegetable(5), Perilla leaves(3), Pepper leaves(3), Mandarin(2), Mustard leaf(2), Radish leaves(2), Water dropwort(2), Celery(2), Marsh mallow(2), Shepherd s purse(2), Crown daisy(1), Cucumber(1), Cherry (1), Grape(1), Jujube(1), Korean cabbage(1) Green & red pepper(6), Mandarin(4), Jujube(2), Leek(2), Brassica leafy vegetable(2), Mustard leaf(1), Mustard green(1), Carrot(1), Lime(1), Radish leaves(1), Water dropwort (1), banana(1), Apple(1), Crown daisy(1), Orange(1), Chamnamul(1), Welsh onion(1), Perilla leaves(1) Brassica leafy vegetable(5), Perilla leaves(4), Korean cabbage(2), Chard(1), Spinach(1), Triazole 17 (3.6%) Chwinamul(1), Chicory(1), Green garlic(1), Mustard leaf(1) a) Samples detected with the same class pesticide of all positive samples Table 10. Risk assessment of pesticides frequently found in agricultural products showing high occurrence of pesticide residues Vegetable Leek Perilla leaves Green & red pepper Cucumber Pesticide Conc.of pesticide (mg/kg) Food daily intake (g/day) ADI a) EDI b) MPI c) %ADI d) %MPI e) mg/kg bw/day mg/person/day Chlorfenapyr Cypermethrin Procymidone Cypermethrin Procymidone Diniconazole Chlorfenapyr Chlorpyrifos Procymidone Chlorothalonil Procymidone Chlorfenapyr Cypermethrin Welsh onion Dimethomorph Procymidone a) Acceptable daily intake (mg/kg bw/day) b) Estimated daily intake (mg/kg bw/day) = {mean of conc. of pesticide (mg/kg) daily food intak (g bw/day)}/1000 c) Maximum permissible intake (mg/person/day) = ADI 64.8 (kg) d) % Acceptable daily intake = (EDI/ADI) 100 e) % Maximum permissible intake = (MPI/ADI) 100

10 Monitoring of Pesticide Residues and Risk Assessment on Agricultural Products Marketed in the Northern Area of Seoul in 도가매우높은농약이었으나 2013년조사에서는 17회검출되어검출횟수가매년감소하는것으로확인되었다. 이는엔도설판이작물잔류성이높고내분비계장애추정물질로활성이높은고독성의농약으로분류되어 2011년 12월생산이금지되었기때문인것으로판단되며추후모니터링검사에서는더욱검출률이감소할것으로예상된다. Table 9에서는검출된농약성분중같은구조를가진동일계열의농약들의검출률을보여준다. Pyrethroid계열의살충제농약들은전체 76건 (16.0%) 의시료에서검출되어가장빈번하게검출되는농약성분으로파악되었으며싸이퍼메쓰린 (44건 ), 비펜스린 (24건 ) 순으로파, 시금치, 부추등의농산물에서검출률이높았다. 외국의사례를살펴보면, Jardim 등 23) 은 pyrethroid계농약중펜프로파스린이피망등의농산물에서 40% 이상의높은검출률을보였다고보고하여이번강북지역모니터링결과와는다빈도검출농약양상이서로다름을확인할수있었다. 인체독성이큰 organophosphate계열의농약들은전체농약검출시료 474 건중 29건 (6.1%) 의시료에서검출되었으며클로르피리포스 (14건), 다이아지논 (5건) 등의농약들이고추, 감귤등의농산물에서가장많이검출되었다. Triazole계열의농약성분들은전체 17건 (3.6%) 검출되었으며그중디니코나졸이엇갈이배추, 들깻잎등에서 14건검출되어가장검출률이높은농약이었다. 잔류허용기준이상으로검출이된농약들을살펴보면살충제 7종, 살균제 7종및생장조절제 1종이었다. 살균제인이프로디온과프로시미돈이 2건씩검출되었으며그외 13종은 1건씩검출되는양상을보였다. 농작물에서부적합검출농약들의기준적용을살펴보면해당작물에검출농약의기준이설정되어있는경우는 6건이었으며검출농약의기준이설정되어있지않아해당작물유사분류의최저기준을적용한경우가 9건이었다. 유사분류의최저기준을적용한경우에는해당농약에대한잔류허용기준이매우낮아지므로부적합처리될가능성이많아지게되며이를방지하기위해서는재배농가들이농약사용지침을반드시준수하도록지도감독을강화하여야할것이다. 잔류농약의위해성평가시민다소비농산물이면서잔류농약검출률이높았던부추, 깻잎, 고추, 오이, 파등 5종의농산물을대상으로검출빈도가높은농약성분들에대한위해성평가를실시하였으며그결과는 Table 10과같다. 일일섭취허용량 (ADI) 대비일일섭취추정량 (EDI) 은 1.050~28.613% 로모든조사대상농산물에서안전한수준으로평가되었다. 파의경우위해성평가대상농약들의 %ADI를살펴보면싸이퍼메쓰린 %, 디메토모르프 % 및프로시미돈 % 로모두 10% 를초과하였다. 반면파를제외한다른농산물의 %ADI는모두 10% 이하로낮은수치를보였다. 하 지만파의 %ADI 값이다른농산물에서의검출농약들에비해높은수치를보이더라도실제성인몸무게를고려한최대섭취허용량대비일일섭취추정량은모두 0.5% 이하로나타나위해성이없는것으로판단되었다. Do 등 26) 의기존의연구결과에서도국내유통농산물 1,064건에대한잔류농약모니터링결과클로르피리포스등 7종의농약에대한위해성평가결과 %MPI가 0.03% 이하로매우안전하다고보고하였다. 다만섭취량이많은농산물의경우미량의농약이검출되더라도일일섭취추정량이커질수있으며이로인하여농산물섭취를통한위해성이증가할수있기때문에계속적인잔류농약모니터링을통한농약잔류량관찰과체계적인위해성평가가요구되어진다. 요약 2013년서울북부지역에서유통되는농산물 2,877건을대상으로 285종의동시분석농약에대한잔류실태를조사하였다. 농약이검출된농산물은 385건 (13.4%) 이었으며잔류허용기준이상으로검출된경우는 15건 (0.5%) 이었다. 농산물분류에따라서는엽경채류 23.4%, 박과이외과채류 21.4%, 엽채류 11.8% 의순으로검출률이높았다. 개별농산물중에서는돌나물 63.6%, 참나물 45.8%, 부추 44.5% 및고추 30.8% 순이었다. 부추와파는부적합률이높았던농산물로각각 5건, 4건이부적합하였다. 2종이상의농약이동시에검출된농산물은 74건 (18.5%) 으로깻잎, 부추, 시금치에서높은빈도를보였다. 전체 45종의검출농약을용도별로분류하면살충제 22종, 살균제 21종, 제초제및생장조절제각 1종이검출되었으며개별농약중에서는프로시미돈, 클로르훼나피르, 싸이퍼메쓰린순으로검출빈도가높았다. 검출농약에대한위해성평가결과 %ADI는 1.050~28.613% 이었으며농산물섭취에따른인체위해성은매우낮은것으로판단되었다. 참고문헌 1. Wang, S., Wang, Z., Zhang, Y., Wang, J. and Guo, R.: Pesticide residues in market foods in Shaanxi Province of China in Food Chem., 138, (2013). 2. Lee, H. J., Choe, W. J., Lee, J. Y., Cho, D. H., Kang, C. S. and Kim, W. S.: Monitoring of ergosterol biosynthesis inhibitor (EBI) pesticide residues in commercial agricultural products and risk assessment. J. Korean Soc. Food Sci. Nutr., 38, (2009). 3. Farid, E. A.: Analyses of pesticides and their metabolites in foods and drinks. Trends anal. chem., 20, (2001). 4. Sana, S. and Cetin, T.: Investigation of pesticide residues in vegetables and fruits grown in various regions of Hatay, Turkey. Food Addit. Contam.: Part B, 5, (2012). 5. Berrada, H., Fernandez, M., Ruiz, M. J., Molto, J. C., Manes,

11 180 Nam Hoon Kim et al. J. and Font, G.: Surveillance of pesticide residues in fruits from Valencia during twenty months (2004/05). Food Control, 21, (2010). 6. WHO: Our planet, out health. Report of the WHO commission on health and environment, Geneva, Switzerland, (1992). 7. Ahn, J. W., Jeon, Y. H., Hwang, J. I., Kim, J. M. Seok, D. R., Lee, E. H., Lee, S. E., Chung, D. H. and Kim, J. E.: Monitoring of pesticide residues and risk assessment for fruits in market. Korean J. Environ. Agric., 32, (2013). 8. Park, K. S., Im, M. H., Choi, D. M., Jeong, J. Y., Chang, M. I., Kwon, K. I., Hong, M. K. and Lee, C. W.: Establishment of Korean maximum residue limits for pesticides in foods. Korean J. Pestic. Sci., 9, (2005). 9. Lee, J. K. and Woo, H. D.: Current status for management of pesticide maximum residue limits in foods. Food Sci. Ind., 43, 2-23 (2010). 10. Kim, C. J., Jung, J. H., Lee, S. J., Park, Y. S. and Ko, S. H.: Calculation of food commodity intake for safety control of pesticide residues. Food Sci. Ind. 43, (2010). 11. Korea Food and Drug Administration. Korea Food Code. (2013). 12. US Environmental Protection Agency, Federal Insecticide, Fungicide and Rodenticide Act (FIFRA). Available from: / Accessed Apr. 21, Lee, J. Y., Choe, W. J., Lee, H, J., Shin, Y. W., Do, J. A., Kim, W. S., Choi, D. M., Chae, K. R. and Kang, C. S.: Research on pesticides residue in commercial agricultural products in J. Fd Hyg. Safety. 25, (2010). 14. Jang, M. R., Moon, H. K., Kim, T. R., Yuk, D. H., Kim, J. H. and Park, S. G.: Dietary risk assessment for pesticide residues of vegetables in Seoul, Korea. Korean J. Nutr. 43, (2010). 15. Jang, M. R., Moon, H. K., Kim, T. R., Yuk,D. H., Kim, E. H., Hong, C. K., Choi, C. M., Hwang, I. S., Kim, J. H., Kim, M. S. and Chae, Y. Z.: Dietary exposure assessment by ages due to pesticide residues in vegetables. Korean J. Pestic. Sci., 16, (2012). 16. Lee, J. Y., Noh, H. H., Lee, K. H., Park, S. H. and Kyung, K. S.: Monitoring of pesticide residues in commercial environment-friendly stalk and stem vegetables and leafy vegetables and risk assessment. Korean J. Pestic. Sci., 16, (2012). 17. Winter, C. K. and Katz, J. M.: Dietary exposure to pesticide residues from commodities alleged to contain the highest contamination levels. J. Toxicol., 2011, 1-7 (2011). 18. Lozowicka, B., Kaczynski, P., Jankowska, M., Rutkowska, E. and Hrynko, I.: Pesticide residues in raspberries (Rubus idaeus L.) and dietary risk assessment. Food Addit. Contam.: Part B, 5, (2012). 19. Korea Food and Drug Administration. Pesticide Residue Database. Available from: pesticides/pesticides_info.jsp. Accessed Apr. 21, Ministry of Health and Welfare, Korea Health Statistics: Korea National Health and Nutrition Examination Survey (2011). 21. Korea Research Institute of Standard and Science. Report of 6 th Size Korea (2010). 22. Kim, Y. H., Park, S. K., Doo, O. J., Kim, O. H., Choi, Y. H., Han, S. H., Lee, C. Y., Kim, Y. K., Han, K. Y. and Chae, Y. Z. : Survey on pesticide residues in commercial agricultural products in the northern area of Seoul. Report of S. I. H. E., 48, (2012). 23. Jardim, A. N. O., and Caldas, E. D.: Brazilian monitoring programs for pesticide residues in food - Results from 2001 to Food Control, 25, (2012). 24. Korea Crop Protection Association. Available from: Accessed May. 15, Han, S. H., Park, S. K., Kim, O. H., Choi, Y. H., Seoung, H. J., Lee, Y. J., Jung, H. J., Kim, Y. H., Yu, I. S., Kim, Y. K., Han, K. Y. and Chae, Y. Z.: Monitoring of pesticide residues in commercial agricultural products in the northern area of Seoul, Korean J. Pestic. Sci., 16, (2012). 26. Do, J. A., Lee, H. J., Shin, Y. W., Choe, W. J., Chae, K. R., Kang, C. S. and Kim, W. S.: Monitoring of pesticide residues in domestic agricultural products, J. Korean Soc. Food Sci. Nutr., 39, (2010).