한국영양학회지 (Korean J Nutr) 2010; 43(4): 404 ~ 412 DOI 10.4163/kjn.2010.43.4.404 서울지역유통채소류섭취에따른잔류농약의위해성평가 * 장미라 1 문현경 2 김태랑 1 육동현 1 김정헌 1 박석기 1 서울시보건환경연구원강남농수산물검사소, 1 단국대학교식품영양학과 2 Dietary Risk Assessment for Pesticide Residues of Vegetables in Seoul, Korea * Jang, Mira 1 Moon, Hyunkyung 2 Kim, Taerang 1 Yuk, Donghyun 1 Kim, Junghun 1 Park, Seoggee 1 1 Gangnam Agro-marin Products Inspection Center, Seoul Metropolitan Government Research Institute of Public Health and Environment, Seoul 138-701, Korea 2 Department of Food Science & Nutrition, Dankook University, Yongin 448-701, Korea ABSTRACT This paper specifically discusses the risk assessment on the pesticide residues in vegetables collected from traditional markets, big marts and departments in the southern part of Seoul. Vegetable samples were 6,583 cases from January to December in 2009. Monte-Carlo simulation was used to calculate the uncertainty for the risk index using pesticide residues, average dietary intake for vegetables and acceptable daily intake. Deterministic risk indexes were 7.33% of diethofencarb, 5.13% of indoxacarb, 3.96% of EPN, 3.92% of diniconazole and 3.09% of chlorothalonil, respectively. And other pesticides were below 3%. Distributions of risk indexes obtained by the Monte-Carlo simulations were similar to the deterministic values, even though the confidence intervals for 95% were very wide. We confirmed that health risks caused by eating vegetables exceeded maximum residue limits of pesticide are very low and the population is generally safe, judging from the risk indexes located between 0.07 to 9.49%. (Korean J Nutr 2010; 43(4): 404 ~ 412) KEY WORDS: pesticide residues, dietary risk assessment, vegetables. 서 농약은현대농업에있어서필수불가결한농업자재로서농산물의생산성제고및품질향상에크게기여하여오늘날풍요로운먹거리의공급이가능하도록하였을뿐아니라, 농산물의생력화를통해노동력과농업생산비절감에중요한역할을함으로써농업인의삶향상에큰공헌을하였다. 이러한장점에도불구하고농약은생물을살멸하는화합물로서정도의차이는있으나독성을가지고있으므로사용하는농업인또는제조공정에종사하는사람의건강을해칠우려가있으며, 적절하게사용하지않을경우작물의약해는물론환경오염을유발시킬가능성이있다. 또한농산물에일정량이상잔류될경우건강에심각한영향을초래하므로농산물을포함한식품중잔류농약문제는사회 접수일 :2010년 6월 10일 / 수정일 :2010년 6월 22일채택일 :2010년 6월 24일 * This work was supported by Seoul Metropolitan Government Research Institute of Public Health and Environment. To whom correspondence should be addressed. E-mail: jangmr@seoul.go.kr 론 적으로중요한이슈가되어왔다. 1) 농약사용의증가로인한부작용을최소화하기위해세계보건기구 (WHO) 를비롯한식량농업기구 (FAO), 미국환경청 (EPA) 등에서는잔류농약의한계치나권고치등을제정하여농산물의관리에이용하고있다. 농약으로인한위해도 (Risk) 는 1일섭취되는식품중각농약성분의함유량을적분하여위해도계수를곱하는방식을취하게된다. 현재까지발표된다수의연구들 2-4) 은위해도를계산하는데필요한요소들의평균값을이용한결정론적인값 (Deterministic value) 으로위해도를제시하고있다. 그러나 1일섭취하는식품은성별, 지역, 직업등에따라분포가다양하고식품중에포함된농약성분은농산물의세척및요리방법에따라잔류량의정도가크게차이가날수있다. 따라서식사섭취로인한농약의위해도는위해도계산에필요한각요소들의분포에기반한확률론적인값 (Stochastic value) 으로제시되어야식품관리정책수립및의사결정도구로적절히이용될수있을것으로판단된다. 따라서본연구에서는 2009 년서울강남지역시장, 대형마트및백화점에서유통되고있는채소류를대상으로잔류농약성분을분석하여그특성을파악하고, 잔류허용기준을초과한채 2010 The Korean Nutrition Society
한국영양학회지 (Korean J Nutr) 2010; 43(4): 404~412 / 405 Table 1. Analyzed pesticides in vegetables Detected by GC-ECD Detected by GC-NPD Detected by LC-UV (DAD) Acetochlor Iprodion Acephate Monocrotophos Acetamiprid Acrinathrin Isoprothiorane Anilofos Myclobutanil Alanycarb Alachlor Mefenacet Azinphos-methyl Napropamide Azoxystrobin Aldrin Methoxychlor Bitertanol Omethoate Benomyl BHC Metobromuron Buprofezin Oxadixyl Benzoximate Bifenox Metolachlor Cadusafos Paclobutrazole Boscalid Bifenthrin Metolachlor Carbophenothion Parathion Carbendazim Bromacil Nitrapyrin Carboxin Parathion-methyl Carbosulfan Bromopropylate Norflurazon Chinomethionate Penconazole Chlorpropham Butachlor Novaluron Chlorfenvinphos Pencycuron Clothianidin Captafol Nuarimol Chlorpyrifos Pendimethalin Cinosulfuron Captan Ofurace Chlorpyrifos-methyl Penthoate Cyazofamid Chlorbenzilate Oxadiazon Cyproconazole Phorate Cyflufenamid Chlordane Oxyfluorfen Cyprodinil Phosalone Cyhalofop-butyl Chlorfenapyr Permethrin Diazinon Phosmet Cymoxanil Chlorfluazuron Phenothrin Dichlorvos (DDVP) Phosphamidone Diflubenzuron Chlorothalonil Probenazole Diethofencarb Phoxim Dimetomorph Cycloprothrin Prochloraz Dimepiperate Pirimicarb Ethaboxam Cyfluthrin Procymidone Dimethenamid Pirimiphos-ethyl Fenhexamid Cyhalothrin Propanil Dimethoate Pirimiphos-methyl Fenpyroxymate Cypermethrin Propisochlor Dimethylvinphos Pretilachlor Ferimzone DDT Pyrethrin Diphenamid Profenofos Fluacrypyrim Deltamethrin Pyridalyl Diphenylamine Prometryne Flufenacet Dichlobenil Pyrimidifen Disulfoton Propamocarb Flufenoxuron Dichlofluanid Quinalphos Edifenphos Propiconazole Fluacrypyrim Dichlofop-methyl Quintozen EPN Prothiofos Flufenacet Dichloran Spirodiclofen Esprocarb Pyraclofos Flufenoxuron Dicofol Tecnazene Ethion Pyrazophos Flumioxazine Dieldrin Tetradifon Ethoprophos Pyridaben Fluquinconazole Diniconazole Thifluzamide Etoxazole Pyridaphenthion Forchlorfenuron Dithiopyr Tolclofos-methyl Etrimfos Pyriminobac-methyl Hexaflumuron Diuron Tolylfluanid Fenamiphos Simazine Imibenconazole Endosulfan Tetraconazole Fenazaquin Simetryn Imidacloprid Endrin Tiadinil Fenitrothion Tebuconazole Iprovalicarb Ethalflurarin Triallate Fenothiocarb Tebufenpyrad Lufenuron Fthalide Triazamate Fenoxycarb Tebupirimfos Methabenzthiazuron Fenamidone Triflumizole Fensulfothion Tebutryne Methoxyfenazide Fenarimol Trifluralin Fenthion Terbufos Oryzalin Fenoxanil Traromethrin Fluazinam Terbuthylazine Oxaziclomefone Fenpropathrin Tefluthrine Fludioxonil Thiazopyr Pentoxazone Fenbuconazole Vinclozolin Flusilazole Thiobencarb Pymetrozine Fenvalerate Zoxamide Formothion Thiometon Pyraclostrobin Fipronil Fosthiazate Thiophanate-methyl Pyrazolate Flonicamid Furathiocarb Triadimefon Pyributicarb Fluazihopbutyl Iprobenfos (IBP) Triadimenol Pyrimethanil Flucythrinate Isazofos Pyriproxyfen Flusulfamide Isofenphos Pyroquilon Flutolanil Kresoxim-methyl Simeconazole
406 / 채소류섭취에따른잔류농약의위해성평가 Table 1. Continued Detected by GC-ECD Detected by GC-NPD Detected by LC-UV (DAD) Fluvalinate Linuron Tebufenozide Folpet Malathion Teflubenzuron Heptachlor Metconazole Thenylchlor Hexaconazole Methidathion Thiacloprid Imazalil Metribuzin Thiamethoxam Indoxacarb Mevinphos Trifloxystrobin Indanofan Molinate Triflumuron Table 2. GC-NPD and GC-μECD conditions used in the determination of the residual pesticides Instrument Agilent 6890N Detector Nitrogen-phosphorus detector μelectiomn capture detector Column DB-1701 14% cyanopropyl phenyl methyl (30 m 320 μm ID 0.25 μm film thickness) HP-5 5% phenyl methyl siloxane (30 m 320 μm ID 0.25 μm film thickness) Oven temp. 100 (2 min) 10 /min 200 (1 min) 10 /min 260 (9 min) 150 (2 min) 10 /min 240 (2 min) 15 /min 270 (25 min) Injection temp. 210 230 Detector temp. 320 280 Gas flow N2 (1.5 ml/min) N2 (1.5 ml/min) Air (60 ml/min) H2 (4 ml/min) Table 3. GC-MSD conditions used in the determination of the residual pesticides Instrument Agilent 6890N Column HP-5MS 5% phenyl methyl siloxane (30 m 250 μm ID 0.25 μm film thickness) Oven temp. 100 (2 min) 10 /min 280 (10 min) Injection temp. 230 Carrier gas He (splitess, 1.0 ml/min) MSD Ionization method Electron impact at 70 ev Ion source temp. 230 Transfer line temp. 280 Scan range 50-550 m/z (2.91 scan/sec) 소류를섭취하였을경우인체위해도를몬테카를로시뮬레이션 (Monte-Carlo Simulation) 을이용하여평가하였다. 재료및방법재료및분석농약 2009 년 1월부터 12월까지서울강남지역시장, 대형마트및백화점등에서유통되고있는채소류 6,583 건에대해잔류농약을분석하였다. 분석농약은 Table 1과같이 258 종을대상으로조사하였다. 시약및기구농약표준품은 Riedel-de Haen사 (Germany), Chem Service (USA), Dr. Ehrenstorfer GmbH (Germany) 그리고 Wako (Japan) 등의제품을사용하였으며, 일반시약 은잔류농약분석용및 HPLC 용을사용하였다. 분석기기는 GC (6890 및 7890, Agilent, USA) 와 HPLC (1100, Agilent, USA) 를사용하였으며, 농약을최종정성확인하기위해 GC/MSD (5975i, Agilent, USA), LC/MSD (6130, Agilent, USA) 를사용하였다. 분석방법시료전처리방법및분석과정은식품공전 5) 중잔류농약시험법과 Lee 등 6) 의동시다성분분석법에따라추출 정제한후 GC-ECD, GC-NPD 및 HPLC-DAD로분석하였으며기기분석조건은 Table 2-4 에나타내었다. 위해성평가인체위해성평가는위해성평가 (risk assessment) 와위해도관리 (risk management) 로나눌수있다. 위해성평
한국영양학회지 (Korean J Nutr) 2010; 43(4): 404~412 / 407 Table 4. HPLC-UV conditions used in the determination of the residual pesticides Instrument Agilent 1200 series Column ZORBAX Eclipse XDB-C18 (5.0 μm, 4.6 150 mm) Detector Diode arrary detector (λ: 254 nm, scan λ: 190-400 nm) Flow rate 1.0 ml/min Column oven 30 Injection vol. 10 μl Mobile phase A (water), B (methanol) Time (min) A (%) B (%) 00.00 70 030 05.00 50 050 10.00 20 080 15.00 05 095 20.00 00 100 23.00 50 050 25.00 70 030 Table 5. ADIs of pesticides from chronic dietary exposure Pesticides ADI (mg/kg/day) Azoxystrobin 0.18 1) 00 Carbendazim 0.03000 Chlorothalonil 0.03000 Chlorpyrifos 0.01000 Diazinon 0.00200 Diethofencarb 0.004 2) 0 Dimethomorph 0.2 3) 000 Diniconazole 0.00200 Endosulfan 0.00600 EPN 0.00140 Etoprophos 0.00040 Indoxacarb 0.0036 1) Kresoxim-methyl 0.36000 Procymidone 0.10000 Tetraconazole 0.004 1) 0 1) Japan, 2) EU, 3) CODEX 가는위험성확인 (hazard identification), 노출평가 (exposure assessment), 양 - 반응평가 (dose-response assessment) 및위해도결정 (risk characterization) 으로세분할수있다. 7) 위험성이확인된독성물질은노출평가와양반응평가를통해인구집단에서위해도의수준을결정하고식품섭취의위험성을판별하게된다. 본연구에서는잔류농약에대한양-반응관계는 KFDA (Korea Food Drug Administration) 잔류농약데이터베이스 8) 의 ADI (Acceptable Dietary Intake) 값을사용하였고 ADI값이설정되지않는물질은일본이나 CODEX, EU 자료를이용하였다 (Table 5). ADI 는동물실험을통해생산된값으로안전계수가고려된상당히엄격한값이며몸무게 (kg) 당허용가능값으로제시된다. 인체노출평가계산에사용한한국성인의평균몸무게는 62.8 kg 9) 을이용하였고, 체중의분포는산업자원부기술표준원에서제공하는자료를바탕으로 triangle distribution 을가정하였다. 따라서평균몸무게 62.8 kg인성인을한국인의대표개인 (Representative person) 으로가정할경우 ADI 는다음식과같이계산할수있다. Acceptable Daily Intake = ADI (mg/kg/day) Body Weight (62.8 kg) (1) 채소류를통해일일섭취되는농약의추정량 (EDI: Estimated Daily Intake) 은채소류에포함되어있는농약의양 ( 농도 ) 과일일섭취하는채소류양의곱이되며, 농약과채소류의종류를고려하면다음과같이나타낼수있다. n k Estimated Daily Intake (mg/day/person) = j j i = 1 j = 1 [(Pesticide Average Conc. (mg/kg)) i (Daily Food Intake (kg/day/person) i] (2) 여기서, i는채소류별잔류농약을, j는채소류일일섭취량을나타낸다. 채소류섭취량은국민건강영양조사 10) 의식품별 1인1일평균섭취량자료를사용하였으며정규분포를가정하였다. 잔류농약이포함된채소류섭취가안전한지의여부는, 식 3과같이허용가능한일일농약섭취량 (ADI) 와일일섭취되는농약의추정량 (EDI) 의비 (Ratio) 를통해결정할수있다. 만약이값이 100 보다크면클수록일일허용가능농약섭취량을많이초과하는것이므로위해하다고판단할수있으며, 100보다작으면작을수록위해가능성이적은것으로판정할수있다. Risk Index = EDI 100 (3) ADI 식 3과같이계산된잔류농약으로인한위해도의불확실성을평가하기위해 Monte-Carlo Simulation (Crystal Ball 2000.5, Decisioneering, Inc., 2004) 을실시하였다. 결 회수율및검출한계각농약성분의회수율은 70~120% 정도로다성분동시분석법으로가능하였고변이율은 10% 미만이었다. ECD 분석 과
408 / 채소류섭취에따른잔류농약의위해성평가 Table 6. Vegetables violated Maximum Residue Limits (MRLs) for pesticides Group Commodity No. of samples No. of violation (%) No. of detection (%) Perilla leaves 0,931 037 (04.0) 227 (24.4) Korean lettuce 0,581 005 (00.9) 053 (09.1) Korean cabbage 0,510 006 (01.2) 040 (07.9) Spinach 0,302 006 (02.0) 049 (16.2) Chicory 0,280 004 (01.4) 021 (07.5) Radish leaves 0,259 003 (01.2) 009 (003.5) Chard 0,246 005 (02.0) 028 (11.4) Leaf Vegetables Mustard green 0,208 028 (13.5) 064 (30.8) Chamnamul 0,196 004 (02.0) 040 (20.4) Marsh mallow 0,185 001 (00.5) 014 (07.6) Crown daisy 0,183 009 (04.9) 020 (10.9) Romaine 00,86 001 (01.2) 011 (12.8) Angelica gigas nakai 00,78 005 (06.4) 012 (15.4) Vitamin 00,65 001 (01.5) 011 (16.9) Pepper leaves 000,6 002 (33.4) 003 (50.0) Others 0,856 013 (01.5) 052 (06.1) Subtotal 4,972 130 (03.3) 654 (13.2) Stalk and stem Welsh onion 0,215 001 (00.5) 014 (06.5) Vegetables Leek 0,100 002 (01.8) 026 (26.0) Sedum 00,87 001 (02.3) 032 (36.8) Water dropwort 00,57 001 (01.7) 002 (03.5) Day lilly 000,5 001 (20.0) 001 (20.0) Others 0,117 000 (00.0) 006 (05.1) Subtotal 0,581 006 (01.1) 0078 (13.4) Root and tuber Beat 000,6 000 (00.0) 001 (16.7) Vegetables Other 0,395 000 (00.0) 000 (00.0) Subtotal 0,401 000 (00.0) 001 (00.2) Fruiting Cucumber 0,144 000 (00.0) 015 (10.4) Vegetables Pepper 0,127 000 (00.0) 032 (25.2) Sweet pepper 00,56 000 (00.0) 005 (08.9) Others 0,302 000 (00.0) 003 (01.0) Subtotal 0,629 000 (00.0) 055 (08.7) Total 6,583 136 (02.1) 834 (12.7) 농약성분의검출한계는 0.0001~0.01 mg/kg 이었고, NPD 분석성분의경우 0.005~0.01 mg/kg, HPLC 분석성분의경우 0.001~0.01 mg/kg이었다. 채소류별분포현황 2009년서울강남지역에유통된채소류 6,583 건에대하여동시다성분잔류농약모니터링결과는 Table 6과같이, 엽채류가 4,972 건 (75.5%) 으로가장많았고과채류가다음으로 629건 (9.6%) 을차지하였으며엽경채류 581건 (8.8%), 근채류 401 건 (6.1%) 이었다. 전체채소류중농약이검출된시료는 834 건으로 12.7% 를차지하였고이중에서잔류허용기준을초과한시료는 136 건으로전체채소류중 2.1% 를차지하였다. 채소류중들깻잎이농약검출 률과허용기준초과율이가장높았으나실제섭취시는유통과정및세척, 조리과정등을거치는동안농약성분의분해로검출량이감소될것으로판단된다. 농약별분포현황유통채소류중농약잔류허용기준을 3회이상초과한농약은 Table 7과같이총 16종이었으며이중 endosulfan 이 24회로가장많았다. 이는전체부적합횟수중 16.0% 를차지하며, 다음으로 diniconazole 22회, paclobutrazol 15회, kresoxim-methyl 9회, ethoprophos 8회, diazinon 7회, chlorpyrifos 5회, carbendazim 5회로잔류허용기준을초과하였다. 이들농약은최저잔류허용기준이대체적으로다른농약보다낮은경우가많았으며, 잔류허용기준을
한국영양학회지 (Korean J Nutr) 2010; 43(4): 404~412 / 409 Table 7. Residual pesticides violated Maximum Residue Limits (MRLs) Classification Pesticides No. of samples violated No. of samples detected Range (mg/kg) Carbofuran 001 001 Chlorfenapyr 001 046 Chlorpyrifos 005 005 0.133-2.922 Cypermethrin 001 037 Diazinon 007 056 0.001-2.821 Endosulfan 024 100 0.010-6.453 Insecticide EPN 004 005 0.074-1.417 Etoprophos 008 009 0.013-0.463 Fenpropathrin 001 003 Indoxacarb 004 012 0.075-10.925 Methidathion 002 004 Prothiofos 001 001 Pyridaben 002 011 Tebupirimfos 001 001 Azoxystrobin 004 059 0.191-12.778 Carbendazim 005 032 0.205-8.641 Chlorothalonil 003 011 0.045-31.039 Cyprodinil 001 001 Diethofencarb 003 059 0.056-11.944 Dimethomorph 004 035 0.387-7.038 Diniconazole 022 052 0.008-2.471 Fludioxonil 002 012 Flutolanil 002 003 Fungicide Iprodione 001 005 Kresoxim-methyl 009 014 0.045-3.856 Metalaxyl 001 020 Metconazole 002 002 Pencycuron 002 007 Procymidone 003 189 0.010-34.625 Tetraconazole 003 009 0.078-3.117 Tolylfluanid 001 003 Trifloxystrobin 001 001 Vinclozolin 002 009 Herbicide Etoxazole 001 001 Pendimethalin 001 002 Growth regulator Paclobutrazol 015 024 0.011-4.332 Total 150 841 초과한상위 3개농약이 40.7% 로거의절반을차지했다. 가장많이검출된농약은 procymidone으로 189건의시료에서검출되었다. 잔류허용기준을초과한농약성분은살충제 14종 62회, 살균제 19종 71회로대다수를차지했으며제초제는 2종 2회이었다. 식물생장조절제는 paclobutrazol 1 종이었으며모두겨자채에서잔류허용기준을초과한것으로나타나농약사용자에대한교육및지도가필요한것으로판단된다. 하지만국민건강영양조사에서겨자채의섭취량이존재하지않아위해성평가에서는제외하였다. 위해성평가위해성평가를위한연구대상농약은농약잔류량분석결과 3회이상잔류허용기준을초과한농약성분으로채소류섭취에의해인체에축적될우려가있는것으로판단되는성분을대상으로하였다. 인체노출평가시채소류섭취에의한농약노출량의평균값사용으로인해발생할수있는불확실성을정량화하기위해채소류의농약잔류량에대한확률밀도함수를판별하였다. 분석한 6,583건농약중잔류농약이허용기준을초과하는경우는모두 150 건으로나타났
410 / 채소류섭취에따른잔류농약의위해성평가 Table 8. Ranking distributions for selecting probability density function of endosulfan in perilla leaves Distribution Andersondarling Chi-square Komogorovsmirnov Lognormal 00.29 1) 00.40 1) 0.15 1) Wibull 00.33 1) 00.00 1) 0.13 1) Pareto 00.55 1) 01.60 1) 0.19 1) Gamma 00.66 1) 00.40 1) 0.22 1) Student s t 01.43 1) 10.00 1) 0.35 1) Max Extreme 01.98 1) 04.80 1) 0.33 1) Logistic 02.31 1) 15.60 1) 0.36 1) Normal 03.06 1) 08.40 1) 0.32 1) Beta 03.08 1) 06.40 1) 0.32 1) Exponential 03.42 1) 07.60 1) 0.40 1) Min Extreme 03.56 1) 24.40 1) 0.39 1) Uniform 14.09 1) 24.40 1) 0.69 1) Triangular 15.23 1) 24.40 1) 0.62 1) 1) can be considered as the first Probability 0.32 0.28 0.24 0.20 0.16 0.12 0.08 0.04 0.00 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 Fit #1: Lognormal distribution Data values Fig. 1. Frequency and probability density function for measured perilla leaves data. 으며이중잔류허용기준을초과하는농약은 endosulfan 외 35종이었고채소류종류는들깻잎외 27종이었다. 그러나잔류농약이허용기준을초과하는건수가많지않아각채소별잔류농약의분포를구하는데한계가있었다. 따라서본연구에서는허용기준을초과하여잔류농약이가장많이검출된들깻잎의 endosulfan 잔류량분포를추정하여다른농약들도각채소에대해동일한정도의표준편차를가지는확률밀도함수가될것이라고가정하였다. Table 8은들깻잎에서 endosulfan의잔류농약이잔류허용기준이상검출된 15건을이용해채소류중에함유된확률밀도함수를구하기위한 Anderson-Darling, Chi-Square, Komogorov- Smirnov 테스트결과이다. Anderson-Darling 의테스트에서는 Lognormal함수가채소류중 endosulfan의잔류량분포로가장적합한것으로나타났으며, Chi-Square와 Komogorov-Smirnov 테스트에서는 Wibull 함수가가장적합한것으로나타났다. 본연구에서는환경측정데이터의가장일반적인분포로알려진 Lognormal 함수를잔류농약의분포로가정하여위해도분석에이용하였다. Fig. 1은들깻잎중 5 4 3 2 1 0 Frequency Fig. 2. Uncertainty analysis for endosulfan using Monte Carlo simulation. Table 9. Comparison between deterministic and stochastic results for the risk index Pesticides Fixed point EDI (mg/day/person) RI (%) Monte-carlo simulation 95 percentiles Azoxystrobin 0.01623 0.14 0.12 0.18 Carbendazim 0.02900 1.54 1.27 1.94 Chlorothalonil 0.05822 3.09 2.54 3.91 Chlorpyrifos 0.00209 0.33 0.27 0.42 Diazinon 0.00123 0.98 0.81 1.24 Diethofencarb 0.01530 7.33 6.02 9.23 Dimethomorph 0.09875 0.79 0.65 0.99 Diniconazole 0.00493 3.92 3.23 4.94 Endosulfan 0.00994 2.64 0.60 9.49 EPN 0.00348 3.96 3.25 5.0 Etoprophos 0.00045 1.80 1.48 2.28 Indoxacarb 0.01161 5.13 4.22 6.49 Kresoxim-methyl 0.01849 0.08 0.07 0.10 Procymidone 0.04060 1.25 1.03 1.58 Tetraconazole 0.00229 0.91 0.75 1.15 에서잔류허용기준을초과한농약의빈도분포와 Lognormal 함수를이용하여나타낸확률밀도함수를보여준다. 각채소류별일일섭취량은표준편차가평균의 10% 인가우스함수로가정하고 EDI 를구하였다. 한편, ADI 를구하는데사용한채소류섭취대상자인한국인의평균몸무게는 62.8 kg 이며, 이를확률밀도함수로가정하기위해최고점은평균몸무게의 1.1, 최하점은평균몸무게의 0.9인삼각형 (Triangular) 분포를사용하였다. Fig. 2은 endosulfan의위해도에대한분포를도시한것으로식 3의위해도계산에사용되는입력인자들의평균을이용하여계산한결정론적 (deterministic) 값은 2.64% 이지만, 각입력변수들의분포를이용하여몬테카를로방법으로불확실성을분석한결과, 평균은 2.71% 중앙값은 1.92%, 최소는 0.25%, 최대는 71.06% 으로나타났다. 따라서위해
한국영양학회지 (Korean J Nutr) 2010; 43(4): 404~412 / 411 도계수가최악의경우라도 (worst case, or conservative assumption) 100보다작은값으로나타나므로, 채소류에잔류하는 endosulfan에의한위해는없는것으로판단할수있다. Table 9는채소류섭취에따른잔류농약의위해도지수를결정론적인값과몬테카를로시뮬레이션에의한확률론적값으로나타낸것이다. 결정론적방법에의한위해도는 diethofencarb 7.33%, indoxacarb 5.13%, EPN 3.96% diniconazole 3.92% chlorothalonil 3.09% 로나타났고기타농약은모두 3% 이하로나타났다. 몬테카를로시뮬레이션분석결과잔류농약의위해도분포는결정론적분석결과와비슷한값을나타내었으나, 95% 신뢰구간의폭은매우넓게나타났다. 그러나위해도지수가 0.07~9.49% 범위에있어농약잔류허용기준을초과한성분에기인한인체위해도는낮은것으로판단되었다. 고찰 농약은독성물질로농산물에사용된다는점에서인체에직접적인위해를가져다줄수있다. 따라서농산물에잔류하는농약의식이섭취량을추정하여인체에대한위해여부를판단하고농약사용에따른식품안전성을확인하는것이필요하다. 본연구에서는서울강남지역시장, 대형마트및백화점등에서유통되고있는채소류를대상으로잔류농약성분을분석하였고, 채소류중잔류허용기준을초과하는비율이높은농약성분을선별하여채소류섭취에의한각농약의인체위해성을파악하고자하였다. 정량적위해평가 (Qualitative risk assessment) 는위해성분의 ADI와추정된섭취량을비교하는방법이사용되고있고 EPA 에서는새로운위해판단지수로 Reference Dose (RfD) 를이용하여비교하는방법을사용하고있다. 11-13) 국내에서는잔류허용기준에근거하여이론적식이섭취량을계산하여 ADI 와비교한결과 chlorpyrifos 등일부성분의비율이높다고보고하였다. 2,14-16) 이러한 ADI 와의비교를통한위해성평가는위해물질의허용량결정과안전사용기준설정을위한기초자료로서의미가있다. 17) 최근잔류농약에대한연구는기본적인농약잔류량을조사하는모니터링제도와더불어위해성평가에초점이맞추어지고있다. 특히미국에서는매년미국식품의약품안전청 (Food and Drug Administration) 에서자국내생산농산물과수입농산물에대한모니터링을실시하고그결과를이용하여식이섭취량에따른위해성평가를실시하고있다. 18) 본연구에서채소류중농약잔류허용기준을초과한농약은 endosulfan이가장많았고, 가장많이검출된농약은 procymidone으로 189건의시료에서검출되었다. 이는김등 19) 이 procymidone 은잔류농약모니터링에서다빈도검출농약이라고국내유통농산물의농약잔류실태모니터링에서보고한결과와유사하였다. 채소류에서잔류허용기준을초과한농약에대해산출한결정론적위해지수는 diethofencarb 7.33%, indoxacarb 5.13%, EPN 3.96%, diniconazole 3.92%, chlorothalonil 3.09% 로나타났고기타농약은모두 3% 이하로나타났다. 몬테카를로시뮬레이션을이용해위해도의불확실성을평가한결과, 잔류농약의위해도분포는결정론적분석결과와비슷한값을나타내었으나, 95% 신뢰구간의폭은매우넓게나타났다. 그러나위해도지수가 0.07~9.49% 범위에있어잔류허용기준을초과한농약성분에기인한인체위해도는낮아대체적으로안전한수준이었다. 미국 17) 에서실시한식이섭취총량조사에서대부분의농약이 ADI 의 1% 이하로나타났다고보고하였고, Ronchin 등 20) 은식품의평균소비자는약 5% 내외, 임산부는 2% 로위해성이낮아진반면, 어린이는 6% 이었다고보고하였다. 일반적으로정확한인체위해성평가는섭취전의식품에대한추정식이섭취량을구해야한다. 따라서채소류의경우세척 조리 가공과정을거치는동안소실되어실제섭취전의농약잔류량은더욱낮아진다. 본연구에서는유통중인채소류를분석한결과를이용하였으므로잔류농약의양은섭취전의양에비해훨씬높았을것이다. 따라서 worst-case로사용된위해성평가에서안전한수준으로나타났으므로서울지역유통채소류의잔류농약에의한위해도도외국의경우와유사한수준으로안전한것으로판단된다. 일반적으로유독성분에대한인체노출량 (human exposure dose) 이 ADI 의 10% 미만일때는위험성을걱정할필요가없고 10% 를초과하게되면정밀조사와철저한법적규제를필요로하며 ADI 의 30% 수준에도달하게되면위험경고를해야되는것으로인식되고있다. 21) 따라서본연구결과가 10% 이내수준을나타내고있긴하지만조리된음식중의농약잔류데이터에근거한것이아니므로, 향후더세밀한식이섭취량평가에대한연구가필요할것으로판단된다. 요약 2009 년 1월부터 12월까지서울강남지역시장, 대형마트및백화점등에서유통되고있는채소류에대해잔류농약을분석하여잔류농약위해성평가를실시하였다. 1) 유통채소류 6,583 건에대하여동시다성분잔류농약모니터링결과, 엽채류가 4,972 건 (75.5%) 으로가장
412 / 채소류섭취에따른잔류농약의위해성평가 높은비율을차지하였으며과채류 629 건 (9.6%), 엽경채류 581건 (8.8%), 근채류 401건 (6.1%) 순이었다. 전체채소류중농약검출율은 12.7% (834 건 ) 이었고, 이중에서잔류허용기준을초과한시료는 2.1% (136 건 ) 으로나타났다. 채소류중들깻잎이농약검출률과허용기준초과율이가장높게나타났다. 2) 유통채소류중농약잔류허용기준을 3회이상초과한농약은총 16종이었으며이중 endosulfan 이 24회로가장많았다. 이는전체부적합횟수중 16.0% 를차지하였으며, 다음으로 diniconazole 22회, paclobutrazol 15회, kresoxim-methyl 9회, etoprophos 8회, diazinon 7회, chlorpyrifos 5회, carbendazim이 5회잔류허용기준을초과하였다. 이들농약은최저잔류허용기준이대체적으로다른농약보다낮은경우가많았으며, 잔류허용기준을초과한상위 3개농약이 40.7% 로거의절반을차지했다. 가장많이검출된농약은 procymidone으로 189건의시료에서검출되었다. 3) 농약잔류량과채소류평균섭취량및 ADI 로부터위해지수 (HI) 를산출하였다. 결정론적방법에의한위해도는 diethofencarb 7.33%, indoxacarb 5.13%, EPN 3.96%, diniconazole 3.92%, chlorothalonil 3.09% 였으며기타농약은모두 3% 이하로나타났다. 몬테카를로시뮬레이션분석결과잔류농약의위해도분포는결정론적분석결과와비슷한값을나타내었으나, 95% 신뢰구간의폭은매우넓게나타났다. 그러나위해도지수가 0.07~9.49% 범위에있어농약잔류허용기준을초과한성분에기인한인체위해도는낮아대체적으로안전한수준으로판단된다. 하지만본연구는채소류에만국한된연구이므로잔류농약이포함된농산물섭취로인한안전성확보를위해서는농약잔류허용기준이합리적으로설정되어야할뿐만아니라위해성평가및모니터링이효과적으로수행되어야할것이다. Literature cited 1) Seoul Metropolitan Government Research Institute of Public Health and Environment. The symposium on the management of toxic materials in food. Present & future of the management for pesticide residues in vegetables ; 2008. p.43 2) Chun OK, Lee YW. A Study on the of Pesticide Exposure by Food Intake. J Fd Hyg Safety 1999; 14(2): 201-215 3) Lee HM, Han JY, Yoon EK, Kim HM, Hwang IG, Choi DM, Lee KB, Won KP, Song IS, Park SE, Shin DC. Cumulative risk assessment of organophosphorus pesticides in the diet. J Fd Hyg Safety 2001; 16(1): 1-26 4) Han KT, Park HJ, Lee KS, Kim IJ, Kim KS, Cho SM. Pesticide residue survey and risk assessment of fruits in Daejeon. Korean J Environ Agric 2002; 21(4): 279-285 5) Korea Food and Drug Administration. Korea Food Code; 2009 6) Lee SM, Michael L, Papathakis, Hsiaoming C, Feng, Gray FH, Joyce EC. Multipesticide residue method for fruits and vegetables. Fresenius J Anal Chem 1991; 339(6): 376-383 7) Pyo HS, Park SR. Environmental analysis & human health risk assessment(1)-analysis & risk assessment of chlorinated disinfection by-products in drinking Water. Analytical Science & Technology 2000; 13(6): 89-96 8) Korea Food and Drug Administration. Pesticide Residue Database. Available from: http://fse.foodnara.go.kr/residue/pesticides/ pesticides_info.jsp; 2010 9) Korea Research Institute of Standard and Science. Report of 5th Size Korea; 2004 10) Ministry of Health and Welfare. The Third Korea National Heaith & Nutrition Examination Survey; 2005 11) EPA. Anticipated residues for chronic dietary exposure assessment for chlorpyrifos RED; 1999 12) EPA. Human risk assessment-chlorpyrifos; 2000 13) EPA. Toxicology chapter for chlorpyrifos; 2000 14) Lee SR, Lee MK, Kim NH. Computation of theoretical maximum daily intake and safety index of pesticides by Korean population, Korean J Food Sci Technol 1995; 27(4): 618-624 15) Lee MG, Lee SR. Computation of theoretical maximum daily intake of pesticides by Korean population. Food Sci Biotecnol 2001; 10(2): 115-122 16) Lee SR, Lee MG. Present status and remedial actions with regard to legal limits of pesticide residues in Korea. Korean J Environ Agric 2001; 20(1): 34-43 17) Lee SR. Pesticides Problems and Regulatory Aspects in USA. Korean J Environ Agric 1991; 10(2): 178-196 18) FDA. Food and Drug Administration pesticides programme-residues monitering; 2000 19) Kim HY, Yoon SH, Park HJ, Lee JH, Gwak IS, Moon HS, Song MH, Jang YM, Lee MS, Park JS, Lee KH. Monitoring of residual pesticides in commercial agricultural products in Koea. Korean J Food Sci Technol 2007; 39(3): 237-245 20) Ronchin M, Mariani F, Visentin S, Colosio C, Salamana M, Carreri V, Maroni M. Risk assessment of dietary pesticide intake and the EDI/ADI ratio in the post marketing phase. 4th European pesticide residues workshop-pesticide in food and drink; 2002 21) Lee MG. Risk assessment of organophosphorus pesticides residues in Korean foods [dissertation]. Seoul: Ewha Womans University; 1995