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1 농약과학회지 (Korean J. Pestic. Sci.) Vol. 21, No. 1, pp (2017) Open Access Online ISSN Print ISSN ORIGINAL ARTICLES 건조채소류의잔류농약실태조사 강경리 * 문수진 김광곤 양용식 이세미 최은아 하동룡 김은선 조배식광주광역시보건환경연구원 Monitoring of Pesticide Residues on Dried Agricultural Products Gyungri Gang*, Sujin Mun, Yongshik Yang, Semi Lee, Euna Choi, Dongryong Ha, Eunsun Kim and Baesik Cho Health and Environment Research Institute of Gwangju, Korea (Received on January 25, Revised on March 15, Accepted on March 15, 2017) Abstract The study was conducted for safety evaluation of 208 kinds of residue pesticides on 200 dried agricultural products, which are distributed in Gwangju. The method of monitoring was the second of Multi Class Pesticide Multi-residue Methods in Korean Food Code, and GC-ECD, GC-NPD, GC-MSD, and LC- MS/MS were used as evaluation equipment to analyze. The residue level in pesticides were 15.5% (31 of 200 samples) and 4 samples exceeded MRLs. 4.5 mg/kg of pyraclostrobin (MRL; 3.0 mg/kg) was detected in red pepper, 1.49 mg/kg of chlorpyrifos (MRL; 0.13 mg/kg) in daikon leaves, mg/kg of pyridalyl (MRL; 0.25 mg/kg) in pepper leaves, 0.98 mg/kg of chlorpyrifos (MRL; 0.05 mg/kg), respectively. Pesticides were found on the 15 samples among the 21 samples of red pepper which is a fruit vegetable, and this resulted in high detection rate of 71%. In addition, pesticides were detected on chwinamul, shitake, siler divaricata, daikon leaves and others within MRLs. The frequent detected kinds of pesticides were insecticide (47.6%), fungicide (33.3%), acaricide (14.3%), nematicide (4.8%) in the order named, and pesticides were methoxyfenozide > pyraclostrobin > azoxystrobin, chlorantraniprole > novaluron, trifloxystrobin in frequent order. Key words Dried agricultural products, monitoring, MRLs, pesticides 서 론 건조채소류는수분이많아서부패하기쉬운채소의저장성과수송을좋게하기위하여수분이적은상태로건조시킨채소이다. 건조중에채소의성분과조직에변화가일어나기때문에, 일단건조시킨채소는물에담가도본래처럼되지않으므로신선채소와는별개의식품이다. 건조로인해저장및가공성이향상되며풍미가증가된다. 예전우리조상들은겨울철부족하기쉬운비타민, 미네랄, 식이섬유가골고루들어가있으며구수한맛과부드러운촉감이특징인건조채소류를각종반찬으로만들어먹곤했다. 또한현대산업사회의병폐를인식하고육체적, 정신적으로건강한삶을영위하려는웰빙족과맞벌이부부및 1인가구가증가하 *Corresponding author ggl21@korea.kr 면서가정간편식 (Home Meal Replacement, HMR) 형태의나물밥시장이급격하게성장하고있으며건조채소류시장도지속적으로성장할것으로예상되고있다. 이에건조채소류의잔류농약안전성문제가대두되고있으며이는국내뿐아니라국제적으로도관심의대상이되고있다 (Park et al., 2009). 농약은병해충및잡초로부터농작물을보호하여식량생산성향상과농작물재배작업의편이성을증대시키는등필수불가결한도구이지만사용되는농약에따라다르기는해도필연적으로농산물및토양에일부잔류하게된다. 안전한먹거리에대한관심이증가하면서독성문제에대한인식또한증가하였으며농산물잔류농약에대한관심또한증가추세이다. 2009년국립농산물품질관리원조사에따르면농산물중유해물질위험에대한인식도가 48.3% 로농약이농식품위해요소중 1위로여기고있는것으로발표한바있으며 (National Agricultural Products Quality Management 49

2 50 강경리 문수진 김광곤 양용식 이세미 최은아 하동룡 김은선 조배식 Service., 2009), 식약처의 2016년식품의약품통계연보에의하면국내농산물의부적합률은 1.21% 로국내유통신선채소류의잔류농약안전성검사는꾸준히이루어지고있는데반해건조채소류에대한잔류농약의정확한실태파악은미흡한상황이다. 나라마다식품에잔류하는농약섭취로인해발생할수있는건강상위해를사전에차단하여안전한식품을제공하고자농산물별농약잔류허용기준을설정하여관리하고있으며우리나라또한식품의약품안전처가식품위생법을근거로농약잔류허용기준을설정하고있으며 2016년 11월현재설정된식품은농산물 451종, 축산물 83종, 인삼 81종으로안전한식품이유통되도록노력하고있다 (Ministry of Food and Drug Safety, 2016b). 대부분농산물에대한잔류허용기준은신선채소류에대한기준으로식품공전상가공식품인신선채소류는잔류농약잠정기준을적용하고있다. 건조채소류에대한과학적인농약잔류허용기준설정을위해서는신선원료채소류중의농약잔류량이건조과정에어떻게변화하는지에대한자료가필요하다. 농약이잔류된농산물은건조, 가공하는동안잔류농약의절대량은분명히감소하며그감소정도는농산물과농약의종류, 건조및가공의조건에따라차이를나타낼수 있다 (Park et al., 2009). 또한신선채소류는건조과정중농약성분이수분이감소됨에따라농축될우려가있어건조농산물의잔류농약위해성에대한조사연구는지속적으로수행해야할과제중하나라고볼수있다. 이에본연구에서는유통되는건조채소류의안전성을확보하고농약잔류허용기준설정의기초자료로활용되기를바라며농약의잔류실태를조사하였다. 재료및방법 실험재료실험에사용된검체는 2016년 1월부터 11월까지광주광역시에위치하고있는양동시장등 7곳의재래시장과 4곳의대형마트, 8곳의온라인쇼핑몰등에서총 200건의건조채소류를구입하였다. 건조채소류별구입내역은 Table 1과같으며수거된검체의비율은엽채류, 과채류, 엽경채류, 근채류순이었으며 (Table 2) 국산 166건과수입산 34건이었다 (Table 3). 분석대상농약및시약 분석대상농약은 GC-ECD, GC-NPD, LC-MS/MS/ 로다 Table 1. The number of samples collected for the monitoring of pesticide residues in dried agricultural products Group Sample (dried) Domestic Imported Eggplant 9 Fruits vegetables Red pepper 19 2 Balsam apple 2 1 Pumpkin 14 Sweet potatostem 17 5 Leaf & stem vegetables Bracken 11 5 Taro stem 17 6 Pepper leaves 6 Cirsium setidens 6 Gomchwi 1 Perilla leaf 1 Leafy vegetables Deodeok leaf 1 Daikon leaves 12 3 Siler divaricata. 5 Bujigaengi 4 Rape 1 Chwinamul 18 2 Root vegetables Balloon flower 2 Slices of daikon 12 1 Stone fruits Jujube 6 Mushrooms Tree ear 1 3 Shitake

3 건조채소류의잔류농약실태조사 51 Table 2. Distribution of 200 samples by dried agricultural products type Type of samples Total Vegetable Leafy Leaf & stem Fruits Root Others a) Domestic Imported a) Domestic : stone fruits (6), mushroom (2), Imported : mushroom (9) Table 3. Distribution of 34 Imported samples by origin Country of origin Number of sample China 29 Myanmar 4 Vietnam 1 성분동시분석이가능한 208종농약이대상이며 (Table 4), 농약표준품은 Dr. Ehrenstorfer (Germany) 와 Wako (Japan) 제품을사용하였다. 분석에사용한추출용시약및용매인아세토니트릴과디클로로메탄, 아세톤, 헥산은잔류농약분석용 Merck (USA) 제품을사용하였다. Table 4. List of pesticides (208 pesticides) Acetamiprid Acrinathrin Boscalid Bromacil Bromobutide Anilofos Azinphos-methyl Cadusafos Captafol Captan BHC(α, β, γ, δ 합계 ) Bifenthrin Carbophenothion Chinomethionat Chlordane Bromopropylate Butocaboxim Chlorothalonil Chlorpyrifos Chlorpyrifos-methyl Carbaryl Carbofuran Clothianidin Cyazofamid Cyflufenamid Chlorfenapyr Chlorobenzilate Cyhalothrin Cymoxanil Cypermethrin Chromafenozide Cinosulfuron DDT (DDE, DDD 포함 ) Deltamethrin Diazinon Cyfluthrin Cyprodinil Dicofol Dieldrin Diethofencarb Cyproconazole Dicloran Dimethoate Dimethomorph Dimethylvinphos Dichlofluanid Dimethenamid Diphenylamine Dithiopyr Edifenphos Dimepiperate Diphenamid EPN Esprocarb Ethaboxam Diniconazole Endrin Ethoprophos Etoxazole Etrimfos Endosulfan (α, β, Sulfate 합계 ) Ethion Fenazaquin Fenbuconazole Fenhexamid Ethiofencarb Fenarimol Fenothiocarb Fenoxanil Fenoxycarb Fenamidone Fenobucarb Fenthion Fenvalerate Ferimzone Fenitrothion Fenpyroximate Fluacrypyrim Fluazinam Fludioxonil Fenpropathrin Flonicamid Flumioxazine Fluquinconazole Flusilazole Fipronil Flufenoxuron Fluvalinate Folpet Forchlorfenuron Flufenacet Flutolanil Heptachlor (epoxide 포함 ) Hexaconazole Hexaflumuron Flusulfamide Fthalide Indanofan Indoxacarb Iprobenfos Fosthiazate Imibenconazole Isazofos Isofenphos Isoprocarb Imazalil Iprovalicarb Lufenuron Malathion Mecarbam Iprodione Kresoxim-methyl Mepronil Metalaxyl Metconazole Isoprothiolane Mepanipyrim Methiocarb Methomyl Methoxychlor Mefenacet Methidathion Molinate Myclobutanil Nitrapyrin Methabenzthiazuron Metolcarb Ofurace Oxadiazone Oxadixyl Methoxyfenozide Nuarimol Paclobutrazol Parathion Parathion-methyl Novaluron Oxaziclomefon Pentoxazone Permethrin Phenthoate Oxamyl Pendimethalin Phosphamidone Pirimicarb Pirimiphos-ethyl Penconazole Phosmet Prochloraz Procymidone Profenofos Phosalone Probenazole Propoxur Prothiofos Pyraclofos Pirimiphos-methyl Propisochlor Pyrazophos Pyributicarb Pyridaben Promecarb Pyrazolate Pyrimidifen Pyriminobac-methyl Pyriproxyfen Pyraclostrobin Pyrimethanil Quintozene Simeconazole Spirodiclofen Pyridaryl Quinalphos Tebufenpyrad Tebupirimfos Teflubenzuron Pyroquilon Tebufenozide Terbuthylazine Tetradifon Thenychlor Tebuconazole Terbufos Thiazopyr Thifluzamide Thiodicarb Tefluthrin Thiamethoxam Tolclofos-methyl Tolylfluanid Tralomethrin Thiacloprid Tiadinil Tricyclazole Trifloxystrobin Triflumizole Thiometon Triazophos Vinclozolin Zoxamide Dichlorvos Triadimefon Trimethacarb Aldicarb Aldrin Benzoximate Triflumuron Azoxystrobin Bendiocarb

4 52 강경리 문수진 김광곤 양용식 이세미 최은아 하동룡 김은선 조배식 시료의추출 식품공전의식품중잔류농약시험법 다종농약다성분분석법 (Multi class pesticide multiresidue methods) 제 2법에따라추출용매로아세토니트릴을사용하였다 (Ministry of Food and Drug Safety., 2016a). 검체를믹서 (DA700-G, Daesung Artlon, Korea) 를이용하여일정크기로분쇄하여균질화후시료약 10 g을정밀히달아혼합추출분쇄기 (SMT PROCESS Homogenizer, JAPAN) 에넣고증류수 50 ml 를넣어 2 시간방치후아세토니트릴 100 ml를넣어 2~3분균질화시킨후부흐너깔대기로여과후여액을 NaCl 10~15 g이들어있는분액여두에넣고흔들어정치후기체크로마토그래프및액체크로마토그래프측정용으로상층액 10 ml를각각취하여 40 o C 이하수욕상에서 1차감압농축하였다. 시료의정제 기체크로마토그래프측정농약은잔류물을 20% 아세톤함유헥산 4mL로용해하고미리헥산 5mL와 20% 아세톤함유헥산 5mL로활성화시킨 SPE-florisil (500 mg/6 ml) 은 Phenomenex (Torrance, CA, USA) 제품에용출시켜받고 20% 아세톤함유헥산 5mL 를용출하여시험관에모아 40 o C 이하수욕상에서 2차감압농축하고아세톤 2mL로녹이고막여과지 (PTFE 0.45 μm) 로여과하여시험용액으로사용하였다. 액체크로마토그래프측정농약은미리디클로로메탄 5mL로활성화시킨 SPE-NH2 (1 g/6 ml) 는 Phenomenex (Torrance, CA, USA) 제품으로 1% 메탄올함유디클로로메탄 4mL와 7mL를유출하여시험관에합하고 40 o C 이하수욕상에서 2차감압농축후 70% acetonitrile 2 ml에녹여멤브레인여과지 (PTFE 0.45 μm) 로여과하여시험용액으로사용하였다. 기기분석잔류농약 208종에대한분석기기로는 GC-ECD (Agilent 7890B, U.S.A), GC-NPD (Agilent 7890B, U.S.A), GC- MSD (Agilent 5977B, U.S.A) 와 LC/MSMS (Thermo TSQ, U.S.A) 를사용하여정성및정량분석하였으며 Table 5 와 Table 6 의조건으로분석하였다. 잔류농약의회수율, 검출및정량한계측정 회수율은검출된농약의표준품을잔류농약이검출되지않은건고추에시료의함유량기준농도가 0.08~0.5 mg/kg 이되도록첨가한뒤 3회반복시험하여측정하였다. 정량한계 (limit of quantification, LOQ) 와검출한계 (limit of detection, LOD) 는각농도별표준용액을사용하여 6회반복분석하여얻은크로마토그램을기초로하여측정하였다. 적정검출한계는 0.05 mg/kg 이내로하였다. 직선성은모든구간이 ~1.000이었으며정량한계와검출한계는표준편차 (σ) 와검량선의기울기 (S) 를구하여다음식에의하여계산하였고 Table 7과같다. 100 정량한계 = σ, 검출한계 = S S 수분함량분석 검체약 10 g 을정밀하게칭량접시에취한후건조기 (JSOF-700T, JSR, Korea) 를사용하여 105 o C에서측정하였으며 (Ministry of Food and Drug Safety, 2016a) 아래의고유계산식을통해수분함량을분석하였다 (Table 8). 수분 (%) = (b c) / (b a) 100 a : 칭량접시의무게 (g) b : 칭량접시와검체의무게 (g) c : 건조후항량이되었을때의무게 (g) 건조채소류에대한잔류허용기준설정 건조채소류잠정기준원칙은기준이설정되어있지않은건조채소류중에서그원료가되는신선채소류의기준이있는경우는아래와같이신선채소류의기준에수분함량을고려하여적용하도록하고있다 (Ministry of Food and Drug Safety, 2016b). 이에따라수분함량을고려하여농약잔류량을산출하였으며, 기준이설정되어있지않은건조채소류는잔류허용기준이설정된채소류중 MRL이가장낮은작물 Table 5. Analytical conditions for analysis pesticides with GC(ECD, NPD, MSD) Analytical Condition Detector GC-ECD GC-NPD GC-MSD Inlet Tem. 250 o C 250 o C 250 o C Oven Tem. 190 o C (0 min) 7 o C/min 290 o C (13 min) 185 o C (0 min) 4 o C/min 240 o C(3 min) 20 o C/min 290 o C (5 min) 190 o C (0 min) 10 o C/min 290 o C (13 min) Det Tem. 300 o C 300 o C 300 o C Column DB-5 DB-5 DB-5MS Flow rate 1.0 ml/min 1.0 ml/min 1.0 ml/min

5 건조채소류의잔류농약실태조사 53 Table 6. LC-MS/MS parameters for the analytical compounds Analytes Elemental composition R.T. Parent ions Quantification ions Confirmation ions (min) (m/z) (m/z) (CE) (m/z) (CE) Trifloxytrobin C 20 H 19 F 3 N 2 O (43v) (17v) Mepanipyrim C 14 H 13 N (37v) (26v) Cymoxanil C 7 H 10 N 4 O (10v) (20v) Boscalid C 18 H 12 Cl 2 N 2 O (16v) (41v) Tricyclazole C 9 H 7 N 3 S (24v) (28v) Chlorantraniliprole C 18 H 14 BrCl 2 N 5 O (14v) (36v) Pyrimethanil C 12 H 13 N (24v) (30v) Lufenuron C 17 H8Cl 2 F 8 N 2 O (20v) (39v) Fluacrypyrim C 20 H 21 F 3 N 2 O (26v) (50v) Bendiocarb C 11 H 13 NO (11v) (20v) Tiadinil C 11 H 10 ClN 3 OS (27v) (29v) Hexaflumuron C 16 H 8 Cl 2 F 6 N 2 O (12v) (39v) Pyraclostrobin C 19 H 18 ClN 3 O (14v) (14v) Methiocarb C 11 H 15 NO 2 S (18v) (18v) Flufenacet C 14 H 13 F 4 N 3 O 2 S (19v) (12v) Ethaboxam C 14 H 16 N 4 OS (22v) (25v) Ethiofencarb C 11 H 15 NO 2 S (16v) (10v) Acetamiprid C 10 H 11 ClN (22v) (40v) Tebufenozide C 22 H 28 N 2 O (23v) (10v) Ferimzone C 15 H 18 N (22v) (24v) Imibenconazole C 17 H 13 Cl 3 N 4 S (31v) (21v) Chromafenozide C 24 H 30 N 2 O (18v) (10v) Oxaziclomefon C 20 H 14 Cl 2 NO (14v) (26v) Methabenzthiazuron C 10 H 11 N 3 OS (16v) (35V) Cinosulfuron C 15 H 19 N 5 O 7 S (18v) - Fluquinconazole C 16 H 8 Cl 2 FN 5 O (19v) (26v) Methomyl C 5 H 10 N 2 O 2 S (12v) (12v) Thenylchlor C 16 H 18 ClNO 2 S (13v) (33v) Pyribenzoxim-Na C 32 H 27 N 5 O (19v) (37v) Thiodicarb C 10 H 18 N 4 O 4 S (20v) (13v) Forchlorfenuron C 12 H 10 ClN 3 O (17v) (33v) Propoxur C 11 H 15 NO (16v) (10v) Carbaryl C 12 H 11 NO (11v) (28v) Novaluron C 17 H 9 ClF 8 N 2 O (15v) (19v) Flufenoxuron C 21 H 11 ClF 6 N 2 O (13v) (31v) Isoprocarb C 11 H 15 NO (15v) (11v) Pyriproxyfen C 20 H 19 NO (16v) (45v) Pyributicarb C 18 H 22 N 2 O 2 S (16v) (18v) Fenproximate C 24 H 27 N 3 O (15v) (46v) Azoxystrobin C 22 H 17 N 3 O (13v) (33v) Dimethomorph C 21 H 22 ClNO (19v) (30v) Thiacloprid C 10 H 9 ClN 4 S (22v) (36v) Carbofuran C 12 H 15 NO (12v) (23v) Spirodiclofen-Na C 21 H 24 Cl 2 O (19v) (8v) Quinoclamine C 10 H 6 ClNO (25v) (35v) Pyrazolynate C 19 H 16 Cl 2 N 2 O 4 S (18v) (33v) Pyroquilon C 11 H 11 NO (22v) (32v) Pentoxazone C 17 H 17 ClFNO (17v) (6v) Benzoximate C 18 H 18 ClNO (7v) (55v) Oxamyl C 7 H 13 N 3 O 3 S (12v) (8v) Aldicarb-NH4 C 7 H 14 N 2 O 2 S (10v) (17v) Teflubenzuron C 14 H 6 Cl 2 F 4 N 2 O (13v) (24v) Methoxyfenozide C 22 H 28 N 2 O (24v) (10v) Metolcarb C 9 H 11 NO (10v) (30v) Cyazofamid C 13 H 13 ClN 4 O 2 S (15v) (10v) Amisulbrom-Na C 13 H 13 BrFN 5 O 4 S (18v) (23v) Clothianidin C 6 H 8 ClN 5 O 2 S (17v) (33v) Thiamethoxam C 8 H 10 ClN 5 O 3 S (9v) (23v) Fenhexamide C 14 H 17 Cl 2 NO (22v) (33v) Flumioxazin C 19 H 15 FN 2 O (14v) (49v)

6 54 강경리 문수진 김광곤 양용식 이세미 최은아 하동룡 김은선 조배식 에대해기준을적용하였다. 신선채소류기준 결과및고찰 건조채소류품목별결과 100 건조채소류수분함량 (%) 100 신선채소류수분함량 (%) 광주지역에서유통되는국산및수입산건조채소류 200 건 (Fig. 1) 을대상으로 Table 1과같이총 208종의농약잔류량을분석하였다. 건조채소류품목별 23종을검사하여그중 9종에서잔류농약이검출 ( 검출률 4.5%) 되었으며 (Table 10), 소분류별로보면과채류 47건중 2건 (4.3%), 엽채류 60 건중 5건 (8.3%), 버섯류 11건중 1건 (9.1%) 에서농약이검출되어버섯류, 엽채류, 과채류순으로높았다. 품목별로보면건가지에서 1건 (11.1%), 건고추 15건 (71.4%), 건고춧잎 3건 (50%), 건곤드레 1건 (16.7%), 무시래기 1건 (6.7%), 건방풍나물 2건 (40%), 건취나물 7건 (35%), 건표고버섯 1건 (14.3%), 건사리 1건 (6.3%) 총 32건 (Fig. 3) 에서농약이검출 (16.0%) 되었다 (Table 9). 건조채소류는수분함량이많고온도가높으면곰팡이가생기는탓에대부분자연환기가잘되는곳에건조 보관하며, 건조등가공과정에농약이분해될수있지만수분함량감소로단위중량당잔류량은증가하는것이일반적이다. 광주농수산물검사소에서신선채소류의잔류농약검사시엽채류와엽경채류의검출률이높았으나신선채소류는과채류의검출률 (51.6%) 이가장높았으며품목별로는건고추의검출률이가장높고다양한농약이검출되었으며건취나물, 건고춧잎, 건방풍나물이뒤를이었다. 특히건고추의경우씻지않고건조, 분쇄하여음식의부재료로쓰이는것이대부분이며한국인의밥상에서없어서는안되는중요한농작물로서전체채소중가장넓은재배면적을차지하는농작물이다 (Kim et al. 2006). 건고추는 21건중 15건에서 pyraclostrobin, novaluron, boscalid, methoxyfenozide, chlorantranilprole, azoxystrobin, thiacloprid, thiamethoxam, cyhalothrin, chlorpyrifos methyl, trifloxystrobin이 검출되었으며 (Table 11) 검출된농약중 pyraclostrobin, methoxyfenozide, azoxystrobin, cyhalothrin, chlorpyrifos methyl, trifloxystrobin 등 6종은 Table 10과같이건고추에대한기준이설정되어있으나나머지 5종의농약에대해서는건고추에대한기준이설정되어있지않아신선농산물의기준에수분함량을측정한값을보정하여잠정잔류량을추정하였다. 건가지는 9건중 1건에서농약이검출되었으며건조물기준이설정되지않아신선농산물의기준에수분함량을측정한값을보정하여기준을설정하였다. 건조엽채류는취나물, 고춧잎, 방풍나물, 곤드레나물, 무시래기순으로잔류농약검출률이높았다. 건조엽채류가잔류농약검출률이높은이유는농작물의중량당표면적이넓어살포된농약의부착량이증가하기때문으로생각된다 (Jeong et al., 2005). 건취나물은 20 건중 7 건에서살충제인 methoxyfenozide가가장많이검출되었으며또한chlo- rantraniprole, azoxystrobin, pyriproxyfen, lufenuron, novaluron, chlorpyrifos, teflubenzuron, chlorfenapyr, myclobutanil이검출되었으며건취나물에서검출된농약은기준이모두설정되지않아농약이검출된다른건조농산물과마찬가지로신선농산물의기준에수분함량을측정한값을보정하여기준을설정하였다. Kim 등 (2007) 은건조취나물 5건중 2건에서 cypermethrin, endosulfan, fenarimol 이검출되어높은검출률을보인다고하였으나이와일치하는농약이없었다. 건고춧잎은 6건중 3건에서 methoxyfenozide, pyridalyl, azoxystrobin이검출되었으며건고춧잎에대한기준은 3종의농약모두설정되어있지않아신선농산물의기준에수분함량을측정한값을보정하여기준을설정하였다. Kim 등 (2007) 은건고춧잎에서 cypermethrin, cyhalothrin, fenvalerate가다양하게검출된다고하였으나전혀다른양상을보였다. 무시래기는 12건중 1건에서 chlorpyrifos가검출되었으며무시래기또한신선농산물의기준에수분함량을측정한값을보정하여기준을설정하였다. Fig. 1. Number of tested dried agricultural products.

7 건조채소류의잔류농약실태조사 55 Table 7. Validation parameters such as linerarity, LOD, LOQ and recoveries of pesticides detected Pesticide Instrument Correlation coefficient (r 2 ) LOD (ug g 1 ) LOQ (ug g 1 ) Recovery (%) Chlorothalonil GC-ECD Chlorfenapyr GC-NPD Chlorpyrifos GC-NPD Chlorpyrifos-methyl GC-NPD Azoxystrobin HPLC-MS/MS Boscalid HPLC-MS/MS Carbofuran HPLC-MS/MS Lufenuron HPLC-MS/MS Methoxyfenozide HPLC-MS/MS Novaluron HPLC-MS/MS Pyraclostrobin HPLC-MS/MS Teflubenzuron HPLC-MS/MS Thiamethoxam HPLC-MS/MS Trifloxystrobin HPLC-MS/MS Myclobutanil GC-NPD Cyhalothrin GC-ECD Pyridalyl GC-ECD Chlorantranilprole HPLC-MS/MS Pyributicarb HPLC-MS/MS Pyrimethanil HPLC-MS/MS Pyriproxyfen HPLC-MS/MS Thiacloprid HPLC-MS/MS 건취나물 2건, 건고추 6건, 건방풍나물 1건, 건고춧잎 1건에서 2가지이상의농약이검출되었다. 이처럼 2가지이상의잔류농약이검출된이유에대해혼합제의농약이사용되거나주변의다른농작물에살포된농약에의오염, 농작물간의교차오염, 저장기간중오염등의원인을제기하였다 (Hong et al., 2011). 위와같이건조채소류에서검출된농약은고추중 6종의농약을제외한대부분기준이설정되어있지않아우리나라가공식품의잔류농약잠정기준적용 (10) 중 2를기준으로식품원재료분류표의소분류내농산물의최저기준을적용하였다. 엽경채류 61건과근채류 15건, 핵과류 6건에서는잔류농약이전혀검출되지않았으며과채류에서도가지, 고추를제외한여주, 호박에서는잔류농약이검출되지않았다. 엽채류는총 60건을검사하여건고춧잎, 건곤드레나물, 무시래기, 건방풍나물, 건취나물 5종 14건에서농약이검출되었고건곰취, 건깻순, 건더덕잎, 건부지갱이, 건유채에서는잔류농약이전혀검출되지않았다. 근채류는건도라지와무말랭이를검사하였으나잔류농약이전혀검출되지않았으며핵과류에서유일하게검사가이루어진건대추는약용식물중가장농약검출률이높고다종농약이검출되는시료로서 검출된농약은 fenvalerate, vifenthrin, chlorpyrifos라는 Yu 등 (2012) 보고와다른양상을보였다. 그러나시료의검사건수가많지않아대표성이있다고하기에는부족함이있다. 건조채소류원산지별결과원산지별신선채소류는 Table 2, 3에나타난것처럼국산및수입산시료를구매, 검사하였으며수입산 34건은중국산이 29건으로가장많고미얀마산토란대 4건에대해검사하였다. 수입산은국내산과달리건고사리, 건고구마대, 건토란대와같은엽경채류가 16건으로가장많은검사가이루어졌으며버섯류가 9건으로많이검사되었다. 수입산건조채소류의잔류농약검출률이국내산보다높을거라는예상과달리수입산건조채소류에서는잔류농약검출이 1건도없었다. 건조채소류중검출농약별결과건조채소류중검출된잔류농약 21종을 Fig. 2에나타내었다. 검출된농약은 methoxyfenozide가 8건, pyraclostrobin이 7건, Chlorantraniliprole이 4건, azoxystrobin이 4건, novaluron 이 3건, trifloxystrobin이 3건, teflubenzuron이 2건, pyributicarb가 2건, chlorpyrifos가 2건, boscalid가 2건이며그외 chlorfenapyr, lufenuron, myclobutanil, pyridalyl, pyrip-

8 56 강경리 문수진 김광곤 양용식 이세미 최은아 하동룡 김은선 조배식 Fig. 2. Number of pesticide residues detected in dried agricultural products. Fig. 3. Number of detected dried agricultural products. Table 8. Moisture content of 200 dried agricultural products Sample (Dried) Moisture 1) (%, fresh, raw) Moisture (%, dried) Sample (Dried) Moisture a) (%, fresh, raw ) Moisture (%, dried) Eggplant Slices of daikon Sweet potato stem Daikon leaves Braken Siler divaricata Red pepper Bujigaengi Gomchwi Balsam apple Perilla leaf Rape Jujube Chwinamul Deodeok leaf Taro stem Balloon flower Shitake Tree ear Pumpkin a) : 농업진흥청국립농업과학원농식품종합정보시스템국가표준식품성분표참조국립농업과학원 (National Institute of Agricultural Sciences) roxyfen, chlorpyrifos methyl, cyhalothrin, thiacloprid, thiamethoxam, pyrimethanil, carbofuran 이각 1건검출되었다 (Table 11). Kim 등 (2007) 은건고춧잎에서 cypermethrin 이검출되는등건조농산물에서 cypermethrin, endosulfan과같은내분비계장애추정물질이검출되었다고보고하였으나본조사에서는검출되지않았다. methoxyfenozide는취나물, 고추, 고춧잎, 곤드레나물, 방풍나물등여러종류의건조농산물에서검출되었으며, azoxystrobin은취나물, 고추, 고춧잎 3가지에서검출되었고 pyraclostrobin, boscalid, chlorpyrifos methyl, cyhalothrin, thiacloprid, thiamethoxam 은고추에서만검출되었으며, chlorfenapyr, lufenuron, myclovbutanil, pyriproxyfen은취

9 건조채소류의잔류농약실태조사 57 Table 9. Number of residual pesticides in dried agricultural products Group Leafy vegetables Fruits vegetables No.of analysis No.of detection Commodity 18 7 Chwinamul Pesticide Methoxyfenozide Chlorantraniliprole Azoxystrobin Pyriproxyfen Lufenuron Novaluron Chlorpyrifos Teflubenzuron Chlorfenapyr Myclobutanil 5 2 Siler divaricata Methoxyfenozide Teflubenzuron Pyributicarb 12 1 Daikon leaves Chlorpyrifos 6 3 Pepper leaves Methoxyfenozide Pyridalyl Azoxystrobin 6 1 Cirsium setidens Methoxyfenozide Red pepper Pyraclostrobin Novaluron Boscalid Methoxyfenozide Chlorantraniliprole Azoxystrobin Thiacloprid Thiamethoxam Cyhalothrin Chlorpyrifos Methyl Trifloxystrobin 9 1 Eggplant Azoxystrobin Pyrimethanil Leaf & stem vegetable 16 1 Bracken Cabofuran Mushroom 11 1 Shitake Trifloxystrobin 나물에서만검출되었다. 특히 pyraclostrobin은고추에서만 7번이나검출되어고추재배과정에서빈번하게사용되는농약으로생각된다. 고추에서여러농약이동시에검출되는주된이유는건고추가일정한수확기동안연속적으로수확하는연속수확작물로서잔류되는농약의종류가다양하고검출율이높다고보고하고있다 (Jung et al. 2012). methoxyfenozide는 benzoylhydrazide insecticide로서저독성이고생태독성 III급이며취나물과고추에사용가능한것으로되어있으나농민들은적용작물과관계없이두루사용하고있음을알수있었다. pyraclostrobin은스트로빌루린 계살균제 (strobilurin fungicide) 로서저독성, 생태독성 I급이며다른스트로빌루린계살균제에비해약해가상당히적은것으로알려져있다. 사용하는작물은대부분과채류가많으며검출또한과채류인고추에서만검출되었다. Chlorantraniliprole은저독성이며취나물과고추에서검출되었고, azoxystrobin은 strobilurin계, 저독성, 어독성급II의살균제로서넓은살균 spectrum 을가지며저농도에서도뛰어난살균력을발휘하여약제살포후에도잎이나과실에약흔이남지않아많이사용되고있는농약이다 (Park et al. 2015). novaluron은 benzoylurea계살충제, 저독성, 생태독성III급의

10 58 강경리 문수진 김광곤 양용식 이세미 최은아 하동룡 김은선 조배식 Table 10. Detected Pesticide found in the dried agricultural products Name of the samples Red Pepper Chwinamul No.of detected Detected pesticide Detection range (mg/kg) MRLs (mg/kg) Criteria Result 7 Pyraclostrobin 0.45~ Pepper Not suitable 2 Novaluron 0.07~ ~4.55 Modified Suitable 2 Boscalid 0.15~ ~17.61 Modified Suitable 2 Methoxyfenozide 0.29~ Pepper Suitable 2 Chlorantranilprole 0.24~ Modified Suitable 2 Azoxystrobin 0.39~ Pepper Suitable 1 Thiacloprid Modified Suitable 1 Thiamethoxam Modified Suitable 1 Cyhalothrin Pepper Suitable 1 Chlorpyrifos methyl Pepper (codex) Suitable 2 Trifloxystrobin 0.28~ Pepper Suitable 7 Methoxyfenozide 0.25~ ~104 Modified Suitable 2 Chlorantranilprole 0.21~ ~35.63 Modified Suitable 1 Azoxystrobin Modified Suitable 1 Pyriproxyfen Modified Suitable 1 Lufenuron Modified Suitable 1 Novaluron Modified Suitable 1 Chlorpyrifos Modified Not suitable 1 Teflubenzuron Modified Suitable 1 Chlorfenapyr Modified Suitable 1 Myclobutanil Modified Suitable 3 Methoxyfenozide 0.16~ Modified Suitable Pepper leaves 1 Pyridalyl Modified Not suitable 1 Azoxystrobin Modified Suitable daikon leaves 1 Chlorpyrifos Modified Not suitable 1 Methoxyfenozide Modified Suitable Siler divaricata 1 Teflubenzuron Modified Suitable 2 Pyributicarb 0.08~ ~0.34 Modified Suitable Cirsium setidens 1 Methoxyfenozide Modified Suitable Eggplant 1 Pyrimethanil Modified Suitable Bracken 1 Cabofuran Modified Suitable Shitake 1 Trifloxystrobin Modified Suitable 곤충생장조절제이며취나물과고추에서검출되었다. trifloxystrobin은 oximinoacetate계, fungicide이며고추와표고버섯에서검출되었다. 유기인계농약은유기염소계에비해지속성이적어비교적쉽게분해되므로잔류의위험이낮은것에반해사람과가축에대한독성이강하고 (Lee et al. 2010) 생산물에대해높은가격이형성된다는단점이있다 (Lee et al. 2011). 검출된성분은 chlorpyrifos와 chlorpyrifos methyl이며 chlorpyrifos 는 3급보통독성, 어독성 1급농약으로물에잘녹지않는무색또는흰색의결정형태이며 chlorpyrifos는바퀴와모기같은가정내곤충들을방제하기위하여사용되는등위생을 위한목적으로도사용되어왔으며, 몇몇제제는토양중에서식하는병해충방제용으로효과적이며 (Ken Hassel. 1991) 곡물, 과일및채소등의작물에대해서도사용된다. chlorpyrifos는건고추에기준이설정되어있을뿐건취나물과무시래기에는사용이등록되지않은농약으로건취나물에서 0.98 mg/kg 검출되었으며이는생물인시금치농약잔류허용기준 0.01 mg/kg을기타미설정건조농산물기준적용방법으로계산한잠정기준 0.05 mg/kg을초과한값이며, 무시래기에서는 1.49 mg/kg 검출되었으며이는생물인시금치농약잔류허용기준 0.01 mg/kg을기타미설정건조농산물기준적용방법으로계산한잠정기준 0.13 mg/kg을초과한값으

11 건조채소류의잔류농약실태조사 59 Table 11. Number of dried agricultural products in Detected Pesticide Detected Pesticide No. of Detection Sample(Dried) Methoxyfenozide 8 Chwinaml2, Red pepper2, Pepper leaf3, Cirsium setidens2, Siler divaricata1 pyraclostrobin 7 Red pepper7 Chlorantraniliprole 4 Chwinaml2, Red pepper2 Azoxystrobin 4 Chwinaml1, Red pepper2, Pepper leaf1 Novaluron 3 Chwinaml1, Red pepper2 Trifloxystrobin 3 Red pepper2, Shitake1 Teflubenzuron 2 Chwinaml1, Siler divaricata1 Pyributicarb 2 Siler divaricata2 Chlorpyrifos 2 Chwinaml1, Daikon leaf1 Boscalid 2 Red pepper2 Chlorfenapyr 1 Chwinaml1 Lufenuron 1 Chwinaml1 Myclobutanil 1 Chwinaml1 Pyridalyl 1 Pepper leaf1 Pyriproxyfen 1 Chwinaml1 Chlorpyrifos methyl 1 Red pepper1 Cyhalothrin 1 Red pepper1 Thiacloprid 1 Red pepper1 Thiamethoxam 1 Red pepper1 Pyrimethanil 1 Eggplant1 Carbofuran 1 Braken1 로상당히높은농도로잔류허용기준을초과하였다. chlorpyrifos methyl은검출된농약중 CODEX에기준이설정된유일한농약으로건고추에대한 MRL 10 mg/kg에 0.95 mg/kg 검출되었다. 검출된농약의제품급성독성이높은정도를비교해보면모두저독성또는보통독성이었으며 carbofuran, chlorfenapyr, chlorpyrifos methyl은보통독성에해당되었다. 농약사용목적에따라분류하면검출된살충제는 cyhalothrin, chlorantraniliprole, thiamethoxam, novaluron, methoxyfenozide, teflubenzuron, thiacloprid, pyriproxyfen, chlorpyrifos, pyridalyl 이며, 살균제는 pyributicarb, myclobutanil, trifloxystrobin, pyrimethanil, boscalid, azoxystrobin, pyraclostrobin 이며살응애제는 chlorfenapyr, chlorpyrifos methyl, lufenuron이고살선충제는 carbofuran로살충제 10종, 살균제 7종, 살응애제 3종, 살선충제 1회가검출되었으며살충제와살균제가주로검출되었다. 건조채소류잔류농약부적합건조채소류중잔류허용기준 (MRL) 을초과한농산물은, 잔류농약이검출된농산물 31건중 4건 (12.9%) 으로나타났다 (Table 12). 건고추에서는 pyraclostrobin이 4.5 mg/kg이검출되었고, 이는건고추의잔류허용기준인 3.0 mg/kg을초과하였다. 건취나물에서는 chlorpyrifos가 0.98 mg/kg이검 출되었으며, 생물엽채류의최저기준인 0.01 mg/kg에건취나물의수분함량을보정하여환산한잠정기준인 0.05 mg/kg 에비해 20배에가까이초과되어검출됨을알수있었다. 건고추잎에서는 pyridalyl이 mg/kg이검출되었다. 이것역시 chlopyrifos와마찬가지로고추잎의기준이없어생물엽채류의 pyridalyl 최저기준인 0.05 mg/kg에건고추잎의수분함량을보정하여환산한값인 0.25 mg/kg을잠정기준으로보면약 153배정도가초과되었다. 무시래기는 chlorpyrifos 가 1.49 mg/kg이검출되어생물엽채류의최저기준과무시래기의수분함량을보정하여얻은잠정기준인 0.13 mg/kg과비교해보면 11배이상으로초과하여검출되었다 (Table 8). 잔류농약이건고추 21건중 15건으로검출이가장많았으며잔류허용기준을초과한농약 1건이검출되었다. 한국농촌경제연구원농업관측정보센터소비자결과 (2004) 우리나라국민은세계에서 1인당소비량이가장많은양념으로고춧가루를소비하고있다 (Jung et al., 2012). Kim 등 (2006) 은풋고추와홍고추, 건고추, 고춧가루의농약잔류실태결과잔류허용기준초과건수가풋고추는 30.0%, 홍고추는 11.1%, 건고추는 66.7%, 고춧가루는 87.5% 로건고추와고춧가루에서잔류허용기준초과율이높았는데이는건고추와고춧가루는건조과정중수분이제거되면서무게가감소하여상대적으로잔류농도가증가한다고추정하였다. 또한 Hong 등 (2011) 은유통중인고춧가루에서잔류농약허용기준

12 60 강경리 문수진 김광곤 양용식 이세미 최은아 하동룡 김은선 조배식 을초과하여부적합인고춧가루는 3건으로부적합률은 2.9% 이며 chlorpyrifos, dicloran, cypermethrin, profenofos, fenitrothion, hexaconazole, diazinon, procymidone이검출되었다고보고하였으며이에대해여름철장마를거치면서고온다습해진기후때문에고추에탄저병, 역병등이많이발생하는시기에이를방지하기위해농약사용량이늘어났을가능성을제기했다. 건고추뿐아니라모든건조채소류의잔류농약은신선채소류의잔류농약보다건조로인한수분이감소함에따라농약잔류량이증가하는것으로판단된다. 본연구에서건조채소류중검출된농약대부분은기준이설정되어있지않아잔류농약잠정기준적용에어려움이있었다. 이에따라유사농산물의최소기준을적용하면서각품목별수분함량을적용하거나측정해보정값을비교해야만했다. 농약보호제지침서에따라농산물별로사용가능한적정농약을선택하고살포해야하는것이올바른방법이나실제로는사용등록이되지않은농약성분이빈번히검출되었다 (Kang et al., 2015) 이에대한개선사항으로건조채소류도신선채소류처럼잔류농약별잔류허용기준에대한보완및추가설정이이루어져야한다고생각된다. 우리나라는 2006년 1월부터신선채소류에대해서농산물생산이력제 (traceability system) 를실시하고있다. 농산물품질관리법에서 농산물이력추적관리 란농산물을생산단계부터판매단계까지각단계별로정보를기록, 관리하여해당농산물의안전성등에문제가발생할경우해당농산물을추적하여원인규명및필요한조치를할수있도록관리하는것이라정의하고있다. 농산물이력추적관리는첫째, 농산물에대한체계적인관리를통해농산물의안전성확보와신뢰성향상으로우리농산물의국제경쟁력강화, 둘째, 유통중인농산물에문제발생시추적을통한신속한원인규명과해당농산물의회수, 셋째, 농산물에대한생산燒? 吟판매단계의정확한정보를제공함으로써소비자의알권리충족을목적으로한다. 그러나건조채소류 200건에대한잔류농약잔류실태조사를실시한결과 4건의건조채소류에서농약의잔류허용기준을초과하여부적합건조채소류에대한생산자및생산지를파악하였으나신선채소류와달리많은어려움이있었다. 신선채소류뿐아니라건조채소류에대해서도생산이력제를도입하여생산자및유통 판매에대한제도개선이필요할것으로사료된다. 감사의글 본연구는광주광역시보건환경연구원 2016년도연구사업의지원으로수행하였습니다. Literature Cited Park, K. S., J. H. Choi, J. H Suh, S. G. Kim, H. K. Lee and J. H. Shim (2009) Studies on the Processing Factors of Pesticide in Dried Carrot from Field Trial and Dipping Test, The Korean Journal of Pesticide Science 13: Lee, K. A., S. T. Kang, O. H. Kim, S. K. Park, K. T. Ha, Y. H. Choi, H. B. Jo and B. H. Choi (2010) Analysis on Pesticide Residue in Medicinal Dried Fruits, The Korean Journal of Pesticide Science 14: Kim, S. D., B. S. Kim, S. G. Park, M. S. Kim, T. H. Cho, C. H. Han, H. B. Jo and B. H. Choi (2007) A Study of Current Syatus on pesticide Residues in Commercial Dried Agricultural Products, KOREAN J. Food Sci. Technol. 39: Park, D. W., A. G. Kim, T. s. Kim, Y. S. Yang, G. G. Kim, G. S. Chang, D. R. Ha, E. S. Kim and B. S. Cho (2015) Monitoring and Safety Assessment of Pesticide Residues on Agricultural Products Sold via Online Websites, The Korean Journal of Pesticide Science 14: Lee, M. J., M. G. Kim, H. R. Jeong, H. J. Yun, N. Y. Kim, H. T. Kim, C. Y. Kim, W. H. Lee and M. H. Yoon (2011) Residual Pesticides in Dried Agricultural Products Collected from Gyeonggi Province, The Korean Journal of Pesticide Science 15: Kim, G.I, H. T. Kim and K. S. Gyung (2006) Monitoring of pesticide residues in peppers from farmgate and pepper powder from wholesale market in chungbuk area and their risk assessment, The Korean Journal of Pesticide Science 10: Jung, Y. J., M. N. Eom, I. H. Heong, J. S. Son, K. A. Kim and S. W. Shin (2012) Removal effect of residual pesticides in red pepper powder by UV irradiation, The Korean Journal of Pesticide Science 16: Jo, S. a., E. H. Kim, K. S. Kim, J. H. Kim and S. G. Park (2009) Change of the Concentration of Pesticide Residues in Pepper Powder by Storage Temperature and Storage Period, The Korean Journal of Pesticide Science 13: National Agricultural Products Quality Management Service (2009) press release. Ministry of Food and Drug Safety (2016a) Korean Food Standard Codex. Ministry of Food and Drug Safety (2016b) Pesticide MRLs in Food. Yu, I. S, S. K. Park, Y. H. Choi, H. J. Seung, H. J. Jung and S. H. Han, (2012) Monitoring of Pesticide Residues in Dried Medicinal Plants used of Food Materials, Journal of Food Hygiene and Safety 27: Hong, H. G, S. W. Shin, K. C. Kim, I. H. Jeong and K. A. Kim (2011) Report of Gyeonggi Province Institute Health & Environment 24: K. A. Hassell (1991) The Biochemistry and Uses of Pesticides, Macmillan Press, Basingstoke, U.K.

13 건조채소류의잔류농약실태조사 61 Jeong, Y. H, J. H. Kim, Y. D. Lee, C. H. Ihm and J. H. Hur, Choishin Nongyakhak (Latest pesticides). Sigmapress, Seoul, Korea, 2005, 19 Kang, N. S., S. C. Kim, Y. J. Kang, D. H. Kim, J. W. Jang, S. R. Won and J. H. Hyun (2015) Monitoring and Exposure Assessment of Pesticide Residues in Domestic Agricultural Products The Korean Journal of Pesticide Science 19: 건조채소류의잔류농약실태조사 강경리 * 문수진 김광곤 양용식 이세미 최은아 하동룡 김은선 조배식광주광역시보건환경연구원 요약본연구에서는 2016 년 1 월부터 11 월까지광주광역시에위치한양동시장등 7 곳의재래시장과 4 곳의대형마트, 8 곳의온라인쇼핑몰등에서총 200 건의건조채소류를구매하여이에대한잔류농약실태를조사하였다. 이중국내산은 166 건, 수입산은 34 건이었다. 수입산은중국 29 건, 미얀마 4 건, 베트남 1 건이었다. 건조농산물을식품원재료의형태로분류해보면국내산은과채류 44 건, 엽경채류 45 건, 엽채류 55 건, 근채류 14 건, 핵과류 6 건, 버섯류 2 건이며수입산은과채류 3 건, 엽경채류 16 건, 엽채류 5 건, 근채류 1 건, 버섯류 9 건이며품목별로는건토란대 23 건, 건고구마대 22 건, 건고추 21 건, 건취나물 20 건, 건고사리 16 건, 무시래기 15 건, 건호박 14 건, 무말랭이 13 건등총 23 품목이었다. 이를검사하여건고추 15 건, 건취나물 7 건, 건고춧잎 3 건, 건방풍나물 2 건, 건가지 1 건, 건곤드레나물 1 건, 무시래기 1 건, 건표고버섯 1 건, 건고사리 1 건등총 9 품목 32 건에서 21 종의농약이검출되었다. 또한건조채소류 4 품목이잔류허용기준을초과하였으며 ( 부적합률 2.0%) 건고추에서 pyraclostrobin 이 4.5 mg/kg (MRL 3.0), 건취나물에서 chlorpyrifos 가 0.98 mg/kg (MRL 0.05), 건고춧잎에서 pyridalyl 이 mg/kg (MRL 0.25), 무시래기에서 chlorpyrifos 가 1.49 mg/kg (MRL 0.13) 으로기준을초과하였다. 색인어 건조채소류, 실태조사, 잔류허용기준, 농약