이아름외. GC-MSD 를이용한유통한약재의잔류농약모니터링 사용되고있다 7). 잔류농약이란농약의성분이자연계에서변화하여생성된분해물질중안정하여장기간잔류하는것으로독성이강한것은농약의유효성분과마찬가지로각종법류에의한규제대상으로되고있다 8). 생약에대해서는보건복지부고시제

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1 韓藥情報硏究會誌 (Korean Herb. Med. Inf.) 2014;2(1): pissn / eissn GC-MSD 를이용한유통한약재의잔류농약모니터링 이아름, 김태희, 장설, 이아영, 최고야, 김호경 * 한국한의학연구원한약자원그룹 Monitoring of Pesticide Residues in Herbal Medicines Distributed by GC-MSD Lee Ahreum, Kim Taehee, Jang Seol, Lee A-yeong, Choi Goya and Kim Ho-kyoung * Herbal Medicine Resources Group, Korea Institute of Oriental Medicine, Daejeon , Republic of Korea Abstract This study was carried out to investigate the pesticide residues in commercial medicinal herbs in Korea in Among a total of 105 samples of 10 different kinds of herbs, 65 samples (10 Kinds) were domestic, and 40 samples (9 Kinds) were imported. To establish pesticide residues (Aldrin, BHC isomer, DDD, DDE, DDT, Dieldrin, Endrin) in commercial herbal medicines, chromatographic equipment was used with the gas chromatography-mass detector for qualitative analysis. The residual pesticides were not founded in both imported and domestic samples. Keywords: commercial medicinal herb, pesticide residue, monitoring 서론최근대체의학으로서한의학에대한관심이높아지고새로운기능성소재를발굴하려는연구가활발하여생약의소비가증가하였고높아진의식수준과더불어유통한약재의품질관리의필요성을야기시켰다 1,2). 한약재는각종동 식물성약재및광물성등의천연원료를사용함에따라수분이나보관온도, 미생물이나충해등으로쉽게오염될가능성이높아오염을막기위한수단으로유해한화학물질을사용하고특히, 재배과정중발생하는병충해와곰팡이등의방제를위해상당량의농약이사용되고검출되어문제가대두되고있다 3,4,5). 한약재의수요량증가로자생약초의채취만으로는공급량이절대부족한현실이어서농가에서직접재배하는양이늘어나게되었고재배자는한약재의생산량의증가와품질향상을목적으로많은농약을사용하는실정이다 6). 농약은병해충및잡초로부터농작물을보호하고고품질의농산물을안정적으로생산하게하여농업소득을증대시킴은물론저장단계에서도 * Correspondence: 김호경 (Kim Ho-kyoung. Tel: Fax: hkkim@kiom.re.kr) Received , accepted

2 이아름외. GC-MSD 를이용한유통한약재의잔류농약모니터링 사용되고있다 7). 잔류농약이란농약의성분이자연계에서변화하여생성된분해물질중안정하여장기간잔류하는것으로독성이강한것은농약의유효성분과마찬가지로각종법류에의한규제대상으로되고있다 8). 생약에대해서는보건복지부고시제 호및식품의약품안전처고시제 호로유기염소제 5종 (aldrin, BHC, DDT, dieldrin, endrin) 에대한기준및분석방법을설정하여생약및생약추출원료의약품의농약잔류량을규제하기시작하였다 9). 잔류농약을분석하기위해일반적으로방해물질을제거하고특정농약성분만을추출하는용매추출법 (liquid liquide extraction, LLE) 을사용한다. LLE법은수용액과추출용매간분배계수의차이를이용하기때문에특별한장치가필요하지않으며극성이광범위한유기화합물에비교적회수율이높다는장점이있어널리이용되고있다 10). 잔류농약을효율적으로분석하기위해서 GC-MSD(mass selective detector) 11,12), AED(atomic emmision detector) 13,14), NPD(nitrogen phosphorous detector) 15), ECD(electron capture detector) 16) 와 FPD(flame photometric detector) 17) 등의다양한검출기를사용하여비교하는연구가보고되어있다. 특히질량분석계 (mass spectrometry) 는화학물질의정성분석이가능한것이가장큰특징이고 target compound 를검출하는데사용되며, 복잡한시료 (complex matrix) 에서미량의잔류농약의확인과정량이가능하다는장점이있다 18). 본논문에서는 GS-MSD를이용하여 10품목 105건국산및수입한약재에대한유기염소제 5종을분석하여농약잔류실태를조사하여소비자에대한농약의안전성과신뢰성을확보하고자한다. 본론 1. 재료및방법 1) 약재전국에유통되고있는국내산및수입산다빈도한약재 19,20) 중 2013년 3월부터 5월까지 10품목 105건 (Table 1) 을대상으로원산지가명시되어있는건조한약재를구입하였다. 105건한약재는최고야박사로부터기원의진위와품질상태를검증받고 mixer(hmf-3000s, Hanil, Seoul, Korea) 로분쇄한후 50mesh의체로쳐서기밀용기에보관하여사용하였다. Table 1. List of the herbal medicines used for monitoring Name of herbal medicines Number of samples Domestic Imported Anemarrhenae Rhizoma ( 지모 ) 6 6 Citri Unshiu Pericarpium ( 진피 ) 9 2 Corydalis Tuber ( 현호색 ) 4 6 Eucommiae Cortex ( 두충 ) 7 4 Forsythiae Fructus ( 연교 ) 6 4 Gardeniae Fructus ( 치자 ) 5 5 Glycyrrhizae Radix ( 감초 ) 5 5 Leonuri Herba ( 익모초 ) 10 - * Lonicerae Folium et Caulis ( 인동 ) 6 5 Polygoni Multiflori Radix ( 하수오 ) 7 3 Total * Herbal medicine is not collected. 46

3 韓藥情報硏究會誌 (Korean Herb. Med. Inf.) 2014;2(1): pissn / eissn ) 시약및기기시료의추출및분석에사용된용매는 Burdick & Jackson(Muskegon, MI, USA) 사의 HPLC급제품을사용하였고, 정제를위한후로리실은 J.T.Baker(Phillipsburg, NJ, USA) 제품을, 그외의시약들은특급시약을사용하였다. 농약표준품 aldrin, BHC isomers, DDD, DDE, DDT, dieldrin 과 endrin은 Dr. Ehrenstorfer(Augsburg, Germany) 에서구입하여사용하였다. 균질화를위해초음파추출기 (Branson 8510, Emerson Industrial Automation, Danbury, CT, USA) 와감압농축기 (Rotary Vacuum Evaporation System, EYELA, Tokyo, Japan) 을사용하였고기기분석을위하여 Gas chromatography mass detector(gc-msd, Shimadzu, Kyoto, Japan) 를사용하였다. 3) 시료전처리 Aldrin, 총 BHC, 총 DDT, dieldrin 및 endrin의분석은식품의약품안전처고시법에따라 21), 분쇄된시료 5g을물 40mL과아세톤 90mL을가하여균질화한후, 감압여과하였다. 여액에포화식염수 50mL, 증류수 100mL 및디클로로메탄 70mL를넣고흔들어섞은다음정치하여층을분리시키고분리된디클로로메탄층은무수황산나트륨을이용하여탈수하고, 농축한후, 헥산 4mL에녹였다. 후로리실카트리지 (6mL, 1g) 에헥산 6mL와헥산 : 아세톤 (8:12) 를유출하여버린후추출액을상단에넣고유출액을수집한후헥산 : 디클로로메탄 : 아세톤 (50:48.5:1.5) 5mL를유출하여버리고유출액을수집한다음수욕상 (40 이하 ) 에서감압농축시켜용매를날려보낸다음 20% 아세톤함유헥산 2mL에녹여시험용액으로사용하였다 (Fig. 1). Fig. 1. Multiresidue analytical method of pesticides in herbal medicines by Ministry of Food and Drug Safety 47

4 이아름외. GC-MSD 를이용한유통한약재의잔류농약모니터링 4) 기기분석조건본실험에서는 GC-MSD를사용하여시료내의잔류농약을분석하였고, 컬럼은 Restek RTX-5MS(30m 0.25mm I.D., 0.25μm df) 를사용하고헬륨을 0.9mL/min 으로흘려주었으며, 컬럼온도는 100 에서 2분간유지하고분당 10 의비율로 280 까지상승시켜 15min 이상유지하였다. 주입구온도는 260 와 Split mode(10:1) 로설정하고인터페이스온도는 280 로설정하였다 (Table 2). Table 2. Operating conditions of GC-MSD for the analysis Factors Operating Condition Column Restek RTX-5MS (30m 0.25mm I.D., 0.25μm df) Carrier gas Flow 0.9mL/min (He) Inj. Temp. 260 Split mode split mode (10:1) Oven Temp. 100 (2min) 10 /min 280 (15min) MS source Temp 결과및고찰 10종 105품목의유기염소제 5종 aldrin, BHC isomers, DDD, DDE, DDT, dieldrin과 endrin을 GC-MSD를이용하여분석하고확인한결과대상농약의 MS spectrum 이표준품과일치하지않아모두불검출로나타났다 (Fig. 2). 원산지별로비교한다른연구들을살펴보면, Cho 등 22) 에서국산생약에서는 154건중 8건 (9.0%), 수입산생약은 97건중 1건 (1.0%), Choi 등 23) 에서국산이 99건중 62건 (22.2%) 과수입품은 133종중 12종 (4.6%) 으로보고되어국산의검출율이더높은것으로나타났다. 수입하는생약의경우, 수입의약품등관리규정 ( 식품의약품안전처고시제 호 ) 에의해통관절차를거치므로국내유통전유해물질검사가이루어지며검사결과에따라유통이차단되어국산의검출율이더높은것으로보고되었는데 6) 본연구결과를통해국내에유통되고있는국산과수입산한약재모두유기염소제 5종의규제와품질검사가비교적잘이루어지고있다고여겨진다. DDT는토양잔류성문제로 1971년에사용이금지된유기염소제농약으로자연계중에서분해과정을거쳐 DDE, DDD 등의대사산물이생성됨에따라대한민국약전등에서규제하고있는데 9) Hwang 과 Lee 24), Jian 등 25) 의연구에서 DDT와 DDE가검출되어지속적인모니터링의필요성을제시하였으나이번모니터링을통해모두불검출인결과를확인할수있었다. Aldrin, dieldrin과 endrin은 1973년에, BHC는 1979년에생산및판매가금지되어사용되지않는농약들이지만 26), 유기염소제농약은잔류기간이매우길기때문에 1980년대초까지는환경중유기염소제농약이극미량이나마검출되었으나 1990년이후에는검출되지않았으므로한약재내에서도검출이되지않은것으로사료된다. 48

5 韓藥情報硏究會誌 (Korean Herb. Med. Inf.) 2014;2(1): pissn / eissn Fig. 2. Chromatograms of pesticide standards and samples by GC-MSD (a) standard, (b) Anemarrhenae Rhizoma, (c) Citri Unshius Pericarpium, (d) Corydalis Tuber, (e) Eucommiae Cortex, (f) Forsythiae Fructus, (g) Gardeniae Fructus, (h) Glycyrrhizae Radix, (i) Leonuri Herba, (j) Lonicerae Folium et Caulis, (k) Polygoni Multiflori Radix. 49

6 이아름외. GC-MSD 를이용한유통한약재의잔류농약모니터링 결론약용식물중잔류농약의안전성을평가하고자국내에유통되고있는 10종 105품목의유기염소제 5종 aldrin, BHC isomers, DDD, DDE, DDT, dieldrin 과 endrin 을 GC-MSD 를이용하여분석하였다. 분석결과대상농약의 MS spectrum 이표준품과일치하지않아분석결과대상농약 5종모두검출되지않았다. 한약재의사용량과수입량이지속적으로증가하고있으므로이에대한안전성확보는국민의건강보호측면에서매우중요하므로양질의한약재가유통되도록유기염소제 5종외에도사용되고있는농약에대한모니터링사업은지속적으로이루어져야한다. 감사의글본연구는한국한의학연구원전통의학소재자원관리시스템구축사업 (K14142) 및 ICT 융합대체한약자원확보사업 (K14410) 의고유생물자원특성평가및대체한약자원발굴연구과제 (K14411) 의지원으로이루어졌으며이에감사드립니다. 참고문헌 1. Yim OK, Han EJ, Chung JY, Park KS, Kang IH, Kang SJ, Kim YJ. The monitoring of some heavy metals in oriental herbal medicines and their intake rates. Analytical Science & Techn ology. 2009;22(2): Kim MK, Hur MH, Lee CH, Jin JS, Jin SK, Lee YJ. Monitoring of residual sulfur dioxide in herbal medicines. Korean Journal of Pharmacognosy. 2004;35(4): Lee HH, Seo JM, Oh MS, Gang IS, Park JJ, Seo KW, Ha DR, Kim ES. A survey on harmful materials of commercial medical herb in Gwangju area. Journal of Food Hygiene and safety. 2010;25(2): Seo CS, Huang DS, Lee JK, Ha HK, Chun JM, Um YR, Jang S, Shin HK. Concentration of heavy metals, residual pesticides and sulfur dioxide of before/after a decoction. Korean Jou rnal of Herbology. 2009;24(1): Heo SK, Cha YY, Kim EG, Cho WH, Lee H, Baik TH, Seo HS, Park HS, Kim BW, Kwon KR, Lee SG, Yoo JS, Sohn YJ, Sun SH, Kang HC, Seo YC. Determination of heavy metals, sulfur dioxide and residual pepsticides in oriental medical materials at Sangji university orie ntal medical hospital. Korean Journal of Oriental Physiology and Pathology. 2008;22(4): Song YM, Kim NH, Kang HG, Ko SK, Kim HS, Yu IS. Monitoring of pesticide residues in commercial herbal medicines. Seoul Metropolitan Government Research Institute of Public Health and Environment Report. 2003;39: Kim HY, Lee SY, Kim CG, Choi EJ, Lee EJ, Jo NG, Lee JM, Kim YH. A survey on the pesticid e residues and risk assessment for agricultural products on the markets in Incheon area from 2010 to Korean Journal of Environmental Agriculture. 2013;32(1):

7 韓藥情報硏究會誌 (Korean Herb. Med. Inf.) 2014;2(1): pissn / eissn Cho HJ, Hwang IS, Choi BH, Bae CH, Kim MH. Determination of residual pesticides in crude drugs. Korean Journal of Pharmacognosy. 2001;32(3): Lee SH, Kim HS, Kim YM, Kim WS, Won YJ, Chae GY, Kim OH, Park HJ, Jeong SW. Monitori ng of pesticide residues in herbal medicines. Journal of the Environmental Sciences. 2006;1 5(8): Choi WJ, Choi GS, Lee HJ, Won YJ, Park HJ, Kim WS. Determination of simultaneous analyti cal method of residual pesticides by gas chromatography. Journal of the Environmental Sciences. 2009;18(12): Hu X, Jianxin Y, Zhigang Y, Lansun N, Yanfei L, Peng W, Jing L, Xin H, Xiaogang C, Yibin Z. Determination of multiclass pesticide residues in apple juice by gas chromatography-ma ss selective detection after extraction by matrix solid-phase dispersion. Journal of AOAC International. 2004;87(4): Mercer GE, Hurlbut JA. A multiresidue pesticide monitoring procedure using gas chromato graphy/mass spectrometry and selected ion monitoring for the determination of pesticides containing nitrogen, sulfur, and/or oxygen in fruits and vegetables. Journal of AOAC Intern ational. 2004;87(5): Tateishi Y, Takano I, Kobayashi M, Tamura Y, Tomizawa S, Sakai N, Kamijo K, Nagayama T, Kamata K. Analysis of pesticides including chlorine in welsh onions and mushrooms using gas chromatography with an atomic emission detector (GC-AED). Shokuhin Eiseigak u Zasshi. 2004;45(6): Lee SM, Wylie PL. Comparison of the atomic emission detector to other element-selective detector for the gas chromatographic analysis of pesticide residues. Journal of Agricultural and Food Chemistry. 1991;39(12): Tang F, Yue Y, Hua R, Cao H. Dispersion microextraction and determination of pesticide residues in medicinal herbs by gas chromatography with a nitrogen-phosphorus detector. Journal of AOAC International. 2006;89(2): Aslan-Sungur G, Gaga EO, Yenisoy-Karakaş S. Estimation of measurement uncertainty of polychlorinated biphenyls, polycyclic aromatic hydrocarbons and organochlorine pesticide s in the atmosphere using gas chromatography mass spectrometry and gas chromatograph y-electron capture detector. Journal of Chromatography A. 2014;1325: Dugo G, Bella GD, Torre LL, Saitta M. Rapid GC-FPD determination of organophosphorus pesticide residues in Sicilian and Apulian olive oil. Food Control. 2005;16: Cajka T, Hajslova J, Lacina O, Mastovska K, Lehotay SJ. Rapid analysis of multiple pesticid e residues in fruit-based baby food using programmed temperature vaporiser injection-lo w-pressure gas chromatography-high-resolution time-of-flight mass spectrometry. Journ al of Chromatography A. 2008;1186: Lee JT. Research on intake of chinese medicine by Korea. MFDS Reserch Paper. 2006; Sin YM, Kim JI, Kim WS, Park KS, Kim JM, Chae KR, Cho DH, Kim DB, Kim OH. Studies on the residual contents of sulfur dioxide in herbal medicines distributed at domestic. Kore 51

8 이아름외. GC-MSD 를이용한유통한약재의잔류농약모니터링 an Journal Oriental Physiology & Pathology. 2007;21(4): Ministry of Food and Drug Safety. The Korean Pharmacopoeia Tenth Edition. MFDS Notific ation. 2013;2(5): Cho HJ, Hwang IS, Choi BH, Bae CH, Kim MH. Determination of residual pesticides in crud drug. Korean Journal of Pharmacognosy. 2001;32(3): Choi YH, Park SK, Kim OH, Seoung HJ, Han SH, Lee YJ, Jeong HJ, Kim YH, Jo HB, Yu IS, Han KY, Chae YZ. Pesticide residues monitoring of medicinal herbs in Seoul. Korean Journal of Pesticide Science. 2011;15(4) Hwang BH, Lee MR. Solid-phase microextraction for organochlorine pesticide residues analysis in chinese herbal formulations. Journal of Chromatography A. 2000;898: Xue J, Hao L, Peng F. Residues of 18 organochlorine pesticides in 30 traditional chinese medicines. Chemosphere. 2008;71(6): Kim JH. Residues of the organochlorine pesticides and heavy metal in culture environment of ginseng on Sangju. Korean Society of Environmental Health and Toxicology. 2004;19(2):

개최요강

개최요강 55 2009. 5. ( ) ( ) < > 1. 1 2. 2. 2. 3 1) 3 2) 3 3) GC-MS 4. 5 1) 5 2) 5 3) ICP-OES 6 3. 7. 7 1) 7 2) 10. 13 1) 1g 13 2),,, 14 3), 15 4),, 15 4. 17 19 < > [ 1] 2 [ 2] ICP-OES 6 [ 3] 13 [ 4] 1g 13 [ 5]