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J. Fd Hyg. Safety Vol. 25, No. 4, pp. 402~409 (2010) Journal of Food Hygiene and Safety Available online at http://www.foodhygiene.or.kr 한약재의약용부위별중금속함량및탕액에서의이행률조사 정삼주 * 강성태 1 한창호 김수진 고숙경 김윤희 김유경 김복순 최병현 서울시보건환경연구원, 1 서울산업대학교 Survey of Heavy Metal Contents and Intake Rates After Decoction in Herbal Medicines Classified by Parts Sam Ju Jung*, Sung Tae Kang 1, Chang Ho Han, Su Jin Kim, Suk Kyung Ko, Yun Hee Kim, Yoo Kyung Kim, Bog Soon Kim, and Byung Hyun Choi Seoul Metropolitan Goverment Research Institute of Public Health and Environment, Department of Food Science and Technology, 1 Seoul National University of Technology (Received August 6, 2010/Revised October 14, 2010/Accepted November 30, 2010) ABSTRACT - The study was conducted to estimate the contents of heavy metal in commercial herbal medicines (1047 samples of 132 species) which were collected from markets in Seoul and to analyze the contents of heavy metals of herbal medicines by classifying them by parts. The samples were digested using microwave method. The contents of heavy metal (Pb, Cd, and As) and Hg were determined using Inductively coupled plasma-mass spectrometer (ICP/ MS). And the contents of Hg were obtained by Mercury analyzer. The average values of heavy metal in herbal medicines were as follows [mean (minimum-maximum), mg/kg]; Pb 0.870 (ND-69.200), As 0.148 (ND-2.965), Cd 0.092 (ND-2.010), and Hg 0.007 (ND-0.137). And the average values of heavy metal by parts in herbal medicines were as follows [mean (minimum-maximum), mg/kg]; Ramulus 2.046 (0.065-4.474), Herba 1.886 (0.048-10.404), Flos 1.874 (0.052-5.393), Cortex 1.377 (0.011-4.837), Radix 1.165 (0.012-70.111), Rhizoma 1.116 (0.016-5.490, Fructus 0.838 (0.017-4.527), Perithecium 0.729 (0.013-4.953), Semen 0.646 (0.006-4.416). The average values of heavy metal of imported herbal medicines except Radix were higher than domestic ones. By decoction of herbal medicines exceeding the tolerances, average intake rates of Pb, As, Cd and Hg were obtained as 6.1%, 40.3%, 4.7%, and 2.2%, respectively. Key words: herbal medicines, heavy metals, ICP-MS, decoction, intake rates. 한약재는 한약 또는 한약제제 를제조하기위한원료로사용되는생약으로서최근생활수준의향상과더불어건강한삶을누리기위한노력이증가하면서질병의치료뿐만아니라약해진체력의회복을위해서한약재를통해건강을유지하려는경향이많아지고있다 1). 또한전세계적으로한약재의사용량이증가되고있으며, 단순히탕이나환제가아닌다류, 기능성식품및음료등의원료로사용됨으로서한약재에대한소비패턴이다양화되고있다 2). 반면에한약재에사용되는농약의종류, 사용량뿐만아니라인체에축적되는잔류량에대한의문과토양오염에의한중금속오염에도관심이고조되고있으며, 특히국가간의다각적교역의증가에따라재배및가공공정들이우리에게잘알려져있지않으므로안전성에대한국민의 *Correspondence to: Sam-ju Jung, Seoul Metropolitan Government Research Insitute of Public Health and Environment Tel : 82-2-968-5091, Fax : 82-2-968-8174 E-mail : twin2000@seoul.go.kr 관심과우려가증가하고있는것이사실이다 3). 또한일부에서는자가처방에의한한약재를이용한민간요법의성행으로인해치명적인결과를초래할가능성을배제할수없다 4). 따라서한약재를가공한상품의안전성과질의중요성이더욱강조되고있는실정이다. 이처럼한약재안전관리의문제점이지속적으로제기된결과식품의약품안전청에서는생약등의중금속허용기준이중금속전체량을합산한총량으로서 30 ppm 이었던것을생약중개별중금속허용기준으로서납 5, 비소 3, 카드뮴 0.3, 수은 0.2 mg/ kg 이하, 생약의추출물과생약만을주성분으로하는제제는총중금속 30 mg/kg이하로하여식품의약품안전청고시제 2005-62호로고시하고, 2006년 4월부터시행하였으며, 고시제 2006-17호에서는검액의습식분해법을추가하는개정을고시하고있다. 한약재중중금속허용기준은한약재원제에함유되어있는중금속의섭취량을규제하고자정하였는데캐나다의경우원재료로사용되는생약의기준 (As:5 mg/kg, Pb:10 mg/kg, Cd:0.3 mg/kg, Hg:0.2 mg/kg) 과최종완제품의 402

Survey of Heavy Metal Contents and Intake Rates After Decoction in Herbal Medicines Classified by Parts 403 기준 (As:0.01 mg/kg/day, Pb:0.02 mg/kg/day, Cd:0.006 mg/ kg/day, Hg:0.02mg/kg/day) 을다르게설정하여완제품의경우더낮은기준값을설정관리하고있다 5). 한약의안전성에문제가되는중금속은인간의활동에의해서도환경에배출될수있는오염물질로서화학적으로는비중이 4이상으로이동성이적어최초로오염되는지역에머무르는경향이강하고, 토양내에수년에서수십년의반감기를가지면서쉽게분해되지않고축적되는특성이있으며개별유해중금속중납, 카드뮴, 비소는발암물질또는발암가능성이높은물질로분류되어있다 6). 한약재에중금속이오염되는경로는도시하수나산업폐수가수계에유입되어수질을오염시킨후한약재로이행되는경우, 산업폐기물등이농경지로유입되어한약재를오염시키는경우, 매연이나분진등대기오염물에함유된중금속이한약재로이행되는경우, 건조나분쇄과정중기기로부터유입되는경우이다. 위와같은경로로유입된중금속은자연적으로쉽게제거되지않아 1차적으로한약재에축적되고, 생육장해를일으켜수확량을감소시키며, 최종적으로동물이나사람이한약재를섭취함으로서체내에축적되어건강장해를유발 시킨다 7). 따라서본연구에서는유통한약재에대한정보부족및중금속오염에대한문제점이대두되는상황에서약재부위별특성과관련된중금속오염정도를파악하여위해성평가활용목적의모니터링을실시하고, 한약재는대부분탕으로끓이거나환제로만들어섭취하므로중금속이과다하게오염된약재를선정하여탕액으로각각만들어제조전과제조후의농도를측정하여중금속의이행률을산정해봄으로써보다구체적인품질관리를위한근거자료를제시하고자한다. 재료및방법 재료본연구에사용한시료는서울지역을중심으로유통되는국내산및수입산한약재중총 132품목 1047건을대상으로하였으며약용부위별로분류한시료의목록은 Table 1 과같다. 시료는균일하게약 300 g을취해 Mixer (FM-681, Hanil, Seoul, Korea) 로분쇄한후 50메시체로친후기밀용기에보관하여사용하였다. Table 1. List of the herbal medicines used for monitoring Part Radix (32) Rhizoma (22) Cortex (9) Ramulus (5) Herba (15) Fructus (23) Semen (19) Flos (5) Perithecium (2) Latin name Achyranthis Radix, Aconiti Lateralis Radix Preparata, Adenophorae Radix, Angelicae Dahuricae Radix, Angelicae Gigantis Radix, Angelicae Tenuissimae Radix, Araliae Continentalis Radix, Astragali Radix, Aucklandiae Radix, Bupleuri Radix, Clematidis Radix, Codonopsis Pilosulae Radix, Dipsaci Radix, Glehniae Radix, Glycyrrhizae Radix et Rhizoma, Osterici Radix, Paeoniae Radix, Platycodonis Radix, Polygalae Radix, Puerariae Radix, Rehmanniae Radix Preparata, Salviae Miltiorrhizae Radix, Saposhnikoviae Radi, Scrophulariae Radix, Scutellariae Radix, Trichosanthis Radix, Sohorae Radix, Curcumae logae Radix, Sanguisorbae Radix, Rehmanniae Radix, Morindae Radix, Polygoni Multiflori Radix Acori Gramineri Rhizoma, Alismatis Rhizoma, Anemarrhenae Rhizoma, Arisaematis Rhizoma, Atractylodis Rhizoma Alba, Atractylodis Rhizoma, Cimicifugae Rhizoma, Cnidii Rhizoma, Coptidis Rhizoma, Curcumae Longae Rhizoma, Cyperi Rhizoma, Dioscoreae Rhizoma, Fritillariae Thunbergii Bulbus, Rhei Undulatai Rhizoma, Sparganii Rhizoma, Zingiberis Rhizoma, Alpiniae Officinari Rhizoma, Drynariae Rhizoma, Imperata Rhizoma, Sinomeni Caulis et Rhizoma, Curcumae Rhizoma, Polygonati Rhizoma Acanthopanacis Cortex, Cinnamomi Cortex, Eucommiae Cortex, Kalopanacis Cortex, Magnoliae Cortex, Mori Cortex, Moutan Cortex, Phellodendri Cortex, Ulmi Cortex Akebia Caulis, Cinnamomi Ramulus, Mori Ramulus, Uncariae Ramulus, Bambusae Caulis in Taeniam Agastachis Herba, Artemisiae Capillaris Herba, Ephedrae Herba, Leonuri Herba, Menthae Herba, Perillae Folium, Pogostemonis Herba, Taraxaci Herba, Visci Herba, Lophatheri Herba, Dendrobii Herba, Cynomorii Herba, Artemisiae Argyi Herba, Epimedii Herba, Siegesbeckiaae Herba Amomi Fructus Rotundus, Amomi Fructus, Aurantii Fructus Immaturus, Chaenomelis Fructus, Corni Fructus, Crataegi Fructus, Forsythiae Fructus, Gardeniae Fructus, Hordei Fructus Germinatus, Longan Arillus, Lycii Fructus, Ponciri Fructus Immaturus, Rubi Fructus, Schisandrae Fructus, Zizyphi Fructus, Zamthoxyli Fructus, Anethi Fructus, Mume Fructus, Hoveniae semen Cum Fructus, Kochiae Fructus, Tribuli Fructus, Xanthii Fructus, Anisi Stellati Fructus Arecae Semen, Cassiae Semen, Castaneae Semen, Coicis Semen, Cuscutae Semen, Massa Medicata Fermentata, Nelumbinis Semen, Persicae Semen, Plantaginis Semen, Psoraleae Semen, Raphani Semen, Thujae Semen, Trichosanthis Semen, Zizyphi Semen, Tritici Levis Semen, Arctii Semen, Myristicae Semen, Alpiniacae Katsumadaii Semen, Armeniacae Semen Carthami Flos, Chrysanthemi Flos, Lonicerae Flos, Schizonepetae Spika, Syzygii Flos Polyporus, Poria Sclerotium

404 Sam Ju Jung et al. 시약중금속분석을위해 ICP/MS 전처리용으로사용한 H 2 O 2, HNO 3 (Electronic grade, Dong Woo Fine Chem., Seoul, Korea) 는모두반도체가공용으로 EP-S급을사용하였다. 중금속표준용액으로 Multi-element standard for ICP/MS (10 µg/mg, Agilent, USA) 와 Hg standard solution (1,000 mg/kg, Kanto Chemical Co., Japan) 을사용하였고, 회수율검정을위해복숭아잎을기본물질로하여조제된미국국립표준연구원의표준인증물질 (1547 : Peach Leaves, NIST- National Institute of Standards & Technology) 을사용하였다. 실험에사용한물은모두초순수제조장치 (MQ Gradient, Millipore, Massachusetts, USA) 로제조한 18.2MΩ 이상의것을사용하였다. 납, 비소, 카드뮴분석시료의분해는곱게분쇄한시료 0.5 g을정밀하게달아마이크로웨이브용 Express Vessel에넣고 70% HNO 3 12mL 를가한후 Hood에서 16시간이상방치하여예비분해를한후 Microwave Digestion System (MARS 5 Version 194A01, CEM, North Carolina, USA) 으로분해하였으며, 600W( 혹은 1200W : Vessel 30개이상일경우 ) Power에서 15분간 200 o C 까지상승시킨후 5분간온도를유지하고, 1분간 210 o C까지상승시킨후 5분간유지하고다시 1분간 220 o C까지상승시킨후 5분간유지하여분해하였다. 분해후방냉, 탈기하고 Vessel 에 H 2 O 2 1mL를가하여탈색시킨후증류수를가하여 50 ml로정용하고여과후시험용액으로사용하였다. 중금속을분석하기위해서는 Octapole Reaction System (ORS) 이부착된 Inductively Coupled Plasma-Mass Spectrometer (Agilent 7500ce, Tokyo, Japan) 를이용하여분석하였으며기기분석조건은 Table 2와같다. 검량선은다원소표준원액을 5% HNO 3 용액으로희석하여 0.5, 1.0, 2.0, 5.0, 10, 20, Table 2. Operating conditions and data acquisition parameters for ICP-MS Parameter Operating conditions Rf power (W) 1,500 Argon gas flow rates Plasma 15.0 L / min Auxiliary 0.27 L / min Carrier 0.85 L / min He gas flow rate 3.0 ml / min Sampling and skimmer cones Nickle Acquisition parameters Quantitative Points / mass 3 Integration time / mass 0.1 sec Mean acquisition time / replicate 7.28 Replicates 3 Mean acquisition time / sample 21.84 sec 50 및 100 µg/kg 농도로조제하여측정하였으며, 시료와동일하게공실험을하여실제시료의중금속함량을구하였다. 수은분석분쇄한시료 50 mg를정밀히달아수은분석기 (Mercury analyzer NIC, MA-2, Nippon Instrument Co., Japan) 를사용해고온으로가열분해하여수은을기화시켜수은포집기에포집, 농축하여측정하는가열기화금아말감법 (Combusion- Gold Amalgamation Method) 으로파장 253.7 nm에서흡광도를측정하여정량분석하였다. 수은표준원액은 0.001% L- cysteine (98%, Nacalai Tesque Inc., Tokyo, Japan) 용액으로희석하여 0.5, 1, 2, 5, 10 및 20 µg/kg이되도록조제한후수은분석기로분석하여검량선을작성하여정량하였다. 수은분석용첨가제로서 HG-MHT, HG-BHT (Nippon Instruments Co., Japan) 을사용하였다. 검출한계및회수율시험무기성분들을동시에분석하기위한분해효율과측정감도를비교하는방법으로표준인증물질 (Certified Reference Materials :CRM's) 을이용하여회수율을측정하였는데 3개이상의시료를분석시료와동일하게전처리한후, 기기로분석하여그평균값을토대로원소별평균값을측정값과비교하여회수율및표준편차를구하고상대표준편차 (RSD : Relative Standard Deviation, %) 를구하였다 8). 검출한계 (LOD, Limit of detection) 와정량한계 (LOQ, Limit of quantitation) 는반응의표준편차와검량선의기울기에근거하는방법에따라표준용액을단계별로 5회반복측정하여평균값으로검량 y를작성하여다음의식에따라계산하였다. LOD = 3.3 σ/ S LOQ = 10 σ/s (σ: 반응의표준편차, S: 검량선의기울기 ) 탕액의조제와중금속측정방법기준을초과한시료를대상으로한탕액조제시약탕기 (DWP-5000M, Dae-Woong, Korea) 를사용하였으며, 임등 9) 과김등 10) 의실험에서사용한방법에따라시료를각각 50 g씩약포지에담고약탕기에넣은후물 800 ml를가해 10분간방치한다음 150분동안탕제를실시하였다. 150분이경과하면바로약탕기를내려식힌후 500 ml의메스실린더에탕액을넣고정제수로정용하고, 그액을흔들어섞은다음 5mL를정확히취한것을검액으로하여사용하였다 결과및고찰 검출한계및회수율측정결과표준인증물질을이용하여측정한평균회수율은납 90.7%,

Survey of Heavy Metal Contents and Intake Rates After Decoction in Herbal Medicines Classified by Parts 405 Table 3. Certified concentration of constituent elements Elements Certified Measured 1) Recovery RSD LOD 4) LOQ Mean SD Mean 2) SD (%) (%) 3) (µg/kg) (µg/kg) R 2 Pb 0.870 0.030 0.789 0.011 90.7 1.4 0.036 1) 0.108 0.9996 As 0.060 0.018 0.062 0.001 103.3 1.6 0.011 0.034 0.9999 Cd 0.026 0.003 0.026 0.001 100.0 3.8 0.035 0.108 0.9999 Hg 0.031 0.007 0.029 0.001 93.5 3.4 0.009 0.033 0.9999 1) Measured ICP MS and Mercury Analyzer 2) Mean values obtained from three measurements. 3) RSD (%) = standard deviation/mean value 100 4) Limit of detection (LOD) = 3.3 σ/s Limit of quantitation (LOQ) = 10 σ/s Table 4. Heavy metal contents in herbal medicines by parts Part Item No. of samples Radix 32 330 Rhizoma 22 141 cortex 9 68 Ramulus 5 41 herba 15 90 Fructos 23 158 Semen 19 164 flos 5 30 Perithecium 2 25 Total 132 1047 1) Mean ± standard deviation 2) Detection range 3) ND : Not Detected Pb As 0.88 ± 3.861 1) (ND-69.200) 2) (ND 3) -2.432) 0.777 ± 0.903 0.164 ± 0.239 (ND-4.618) (ND-1.803) 1.166 ± 1.157 0.113 ± 0.134 (ND-4.399) (ND-0.724) 1.818 ± 1.325 0.082 ± 0.107 (0.028-4.405) (0.001-0.600) 1.532 ± 1.534 0.233 ± 0.421 (ND-7.190) (0.002-2.965) 0.661 ± 0.858 0.119 ± 0.272 (ND-4.098) (ND-2.423) 0.552 ± 0.305 0.048 ± 0.082 (ND-4.370) (ND-0.600) 1.495 ± 1.299 0.267 ± 0.337 (ND-4.290) (ND-1.286) 0.592 ± 1.124 0.071 ± 0.121 (ND-4.644) (ND-0.510) 0.870 ± 2.345 0.148 ± 0.255 (ND-69.200) (ND-2.965) Cd 0.090 ± 0.105 (ND-0.883) 0.167 ± 0.255 (ND-2.010) 0.088 ± 0.091 (ND-0.420) 0.136 ± 0.176 (0.003-0.810) 0.107 ± 0.103 (0.003-0.461) 0.053 ± 0.061 (ND-0.240) 0.043 ± 0.052 (ND-0.250) 0.092 ± 0.080 (0.001-0.340) 0.057 ± 0.144 (0.001-0.610) 0.092 ± 0.144 (ND-2.010) Hg 0.007 ± 0.009 (ND-0.081) 0.007 ± 0.011 (ND-0.093) 0.009 ± 0.010 (ND-0.063) 0.010 ± 0.008 (0.001-0.031) 0.013 ± 0.012 (ND-0.059) 0.006 ± 0.006 (ND-0.039) 0.003 ± 0.003 (ND-0.017) 0.021 ± 0.026 (ND-0.137) 0.009 ± 0.010 (0.001-0.037) 0.007 ± 0.010 (ND-0.137) Total 1.165 ± 3.939 (0.012-70.111) 1.116 ± 1.083 (0.016-5.490) 1.377 ± 1.197 (0.011-4.837) 2.046 ± 1.420 (0.065-4.474) 1.886 ± 1.916 (0.048-10.404) 0.838 ± 1.001 (0.017-4.527) 0.646 ± 0.598 (0.006-4.416) 1.874 ± 1.536 (0.052-5.393) 0.729 ± 1.296 (0.013-4.953) 1.116 ± 2.461 (0.006-70.111) 비소 103.3%, 카드뮴 100%, 수은 93.5% 였다. 검출한계와정량한계결과납, 비소, 카드뮴의검량선은 0.5-100 µg/kg 농도에서납의경우 R 2 = 0.9996, 비소와카트뮴은 R 2 =0.9999 로나타났으며, 수은의검량선은 0.5-20 µg/kg 농도에서 R 2 = 0.999로양호한직선성을보였다. 또한납, 비소, 카드뮴및수은의검출한계는 0.036, 0.011, 0.035, 0.009 µg/kg, 정량한계는 0.108, 0.034, 0.108, 0.033 µg/kg로이는고시에따른생약의개별중금속기준보다훨씬낮은값으로분석결과의타당성이증명되었다 (Table 3). 약용부위별중금속함량평가약용부위별로납, 비소, 카드뮴, 수은의함량을측정한 결과 (Table 4), 전체시료의중금속평균함량은납 0.870 mg/ kg, 비소 0.148 mg/kg, 카드뮴 0.092 mg/kg, 수은 0.007 mg/ kg이고, 검출범위는납 ND-69.200 mg/kg, 비소 ND-2.965 mg/ kg, 카드뮴 ND-2.010 mg/kg, 수은ND-0.137 mg/kg로나타났다. 약용부위별납의평균함량은줄기류 (1.818) > 잎류 (1.532) > 화류 (1.495) > 표피류 (1.166) > 뿌리류 (0.880) > 뿌리줄기류 (0.777) > 열매류 (0.661) > 버섯류 (0.592) > 종자류 (0.552) 순으로오염정도가높은것으로나타났으며, 검출범위를살펴보면다른부위에비해잎류의검출범위가 ND-7.190 mg/kg로넓게나타나중금속중납의개별기준이 5 mg/kg인것을감안할때잎류의납에대한오염정도가높았다. 이는납의함량이잎, 줄기, 꽃과같은지상부가지하부보다유의적인

406 Sam Ju Jung et al. Fig. 1. Heavy metal contents of herbal medicines based on the using parts and production area. Domestic 345 samples of 56 spieces and imported 702 samples of 76 species were tested. 수준에서높았고, 납의기준을초과한시료도지상부에서더많았다는김등 12) 의연구와비슷한결과를나타내었다. 반면뿌리류의경우납평균함량이 0.880 mg/kg인데반해서검출범위는 ND-69.200 mg/kg으로매우넓게나타났는데이는검사시료중국산시호 1건에서납의함량이 69.200 mg/ kg로높게검출되어납의검출범위와평균함량에영향을미친것으로보인다. 비소의경우잎류와화류가각각 0.233, 0.267 mg/kg으로다른부위에비해평균함량이높았고, 검출범위는뿌리류 ND-2.432, 잎류 0.002-2.965, 열매류가 ND- 2.423 mg/kg으로다른부위에비해높게나타났다. 카드뮴의평균함량을비교한결과다른부위에비해뿌리줄기류, 줄기류, 잎류의평균함량이높게나타났다. 검출범위는뿌리줄기류가 ND-2.01 0mg/kg으로상당히높았으며뿌리류 ND- 0.883, 표피류 ND-0.420, 줄기류 0.003-0.810, 잎류 0.003-0.460, 열매류 ND-0.240, 종자류 ND-0.250, 화류 ND-0.340, 버섯류 ND-0.610 mg/kg 으로시료대부분이카드뮴개별기준인 0.3 mg/ kg 수준을포함하는넓은범위를나타내었다. 이것은카드뮴이대부분의시료에서일정량고르게검출되었음을의미하는것으로이는카드뮴함량이대부분의시료에서고르게나타났다는김등 11) 의연구결과와비슷한경향을보였다. 수은의경우잎류 0.013, 화류 0.021 mg/kg를제외하고대부분이전체평균 0.007 mg/kg보다낮거나비슷한수준을보였다. 약용부위에따른개별중금속의합을살펴보면줄기류 (2.046) > 잎류 (1.886) > 화류 (1.874) > 표피류 (1.377) > 뿌리류 (1.165) > 뿌리줄기류 (1.116) > 열매류 (0.838) > 버섯류 (0.729) > 종자류 (0.646) 의순으로오염정도를나타내었다. 이들결과는약용부위별개별중금속의합이종자류와열매류는낮으나줄기류, 화류, 잎류에서중금속오염이높게나왔다는김등 12) 의연구결과와유사하였다. 이는약용작물스스로토양으로부터중금속을흡착하는능력에따라함량이달라질수있으며, 농약의경우작물표면적이넓을수록잔류 성이높은것과같이약용작물의표면적과중금속농도와도어느정도상관성이있을것으로보인다. 납, 비소, 카드뮴, 수은을합한전체중금속함량을기준으로하여약용부위와산지별로농도를비교했을때 (Fig. 1) 뿌리류를제외한다른부위에서모두국내산보다수입산의함량이높았으며, 특히뿌리줄기류, 잎류, 화류, 버섯류, 열매류는국내산 (0.668, 1.133, 0.876, 0.278, 0.496 mg/kg) 과수입산 (1.418, 2.296, 2.302, 0.842, 1.032 mg/kg) 의함량차이가 2배이상나는것으로나타났다. 이는한등 13~15) 의연구에서수입산한약재가국내산한약재보다대부분중금속함량이높은것으로조사된결과와일치하였다. 개별중금속기준에의한기준초과한약재조사지금까지분석한한약재총 132종 1047건중식품의약품안전청기준을초과한한약재는 23품목 34건으로비소와수은에서기준을초과한것은없었으며, 납의경우국내산한약재 1건 ( 시호 ) 과수입산한약재 4건 ( 한련초, 희렴, 애엽, Fig 2. Distribution of herbal medicines which exceeded individual heavy metal standards. Herbal medicines were classified by the using part.

Survey of Heavy Metal Contents and Intake Rates After Decoction in Herbal Medicines Classified by Parts 407 파극천 ) 으로나타났고, 카드뮴은국내산 4건 ( 포공영, 인진호, 갈근, 시호 ) 과창출, 속단, 계지등수입 27건으로나타났다. 시호와희렴의경우납과카드뮴이함께기준을초과하였다. 기준이초과된한약재 34건중국내산 (12%) 에비해수입산 (88%) 이차지하는비율이높았으며, 부위별로살펴보면 34품목중뿌리줄기류가 11건 (32%) 으로가장많았고, 뿌리류가 9건 (27%), 잎류 8건 (24%), 줄기류 3건 (8.8%) 및버섯류 2건 (5.9%), 표피류가 1건 (2.9%) 으로뿌리줄기류를포함한뿌리류가거의 60% 를차지하는것으로나타났다 (Fig. 2). 이중파극천을제외하고뿌리류와뿌리줄기류의 19건모두가카드뮴의기준을초과하는것이었고이중시 호와갈근을제외한나머지시료모두수입인것을감안할때재배지토양과카드뮴과의상관성을짐작할수있었다. 또한재배지토양과한약재중의중금속농도가비례관계를보인다는이등 16) 과박등 17) 의보고처럼한약재는자연환경속에서재배, 생산되므로환경오염의영향을받고중금속에오염될가능성이크므로그원인분석과함께운반, 수송, 보관중의적절한관리와검사의질적향상이요구되며, 수입하는지역의토양에대한물리화학적특성과재배환경을분석하여카드뮴오염에대한연구가필요할것으로보인다. Table 5. Intake rates of heavy metals after decoction Part Sample name Herba (8) Radix (9) Rhizoma (11) Ramulus (3) Perithecium (2) Intake rate(%) Pb As Cd Hg Total Taraxaci Herba 2.8 2.2 14.6 0.0 4.0 Ecliptae Herba 0.5 18.0 3.3 0.0 1.3 ArtemisiaeIwayomogii Herba 43.5 70.0 4.0 0.0 17.6 Siegesbeckia Herba 4.3 8.0 2.2 0.0 4.9 Siegesbeckia Herba 3.2 21.7 2.7 0.0 4.2 Agrimoniae Herba 2.2 36.4 2.3 0.0 4.1 Artemisiae Capillaris Herba 14.2 85.3 9.3 0.0 13.7 Artemisiae Argyi Folium 4.9 34.1 9.1 0.0 13.3 Bupleuri Radix 0.1 13.8 1.6 0.0 0.2 Linderae Radix 25.0 90.0 10.0 0.0 15.8 Puerariae Radix 16.9 66.7 11.5 0.0 15.8 Aucklandiae Radix 2.9 42.9 4.3 12.5 4.5 Curcumae Radix 3.3 50.8 3.4 0.0 5.0 Dipsaci Radix I 4.1 11.5 5.3 0.0 7.2 Dipsaci Radix II 3.2 17.9 3.4 0.0 5.2 Dipsaci Radix III 0.8 20.1 6.2 0.0 6.0 Morindae Radix 0.6 11.6 0.0 5.9 1.1 Curculiginis Rhizoma 3.9 19.3 4.4 16.7 6.2 Belamcandae Rhizoma 0.6 6.3 4.7 0.0 2.7 Atractylodis Rhizoma I 1.2 28.6 2.3 0.0 2.6 Atractylodis Rhizoma II 3.9 47.4 6.3 0.0 6.4 Atractylodis Rhizoma III 4.8 33.2 9.5 0.0 7.5 Curcumae Rhizoma I 0.3 31.3 1.9 0.0 1.7 Curcumae Rhizoma II 10.3 83.3 8.0 0.0 10.2 Drynariae Rhizoma I 3.5 27.5 3.5 0.0 4.6 Drynariae Rhizoma II 0.0 84.4 5.2 0.0 5.1 Coptidis Rhizoma I 7.7 46.4 11.5 0.0 10.3 Coptidis Rhizoma II 9.7 65.9 8.2 11.1 11.4 Cinnamomi Ramulus I 13.3 81.7 0.0 0.0 11.6 Cinnamomi Ramulus II 7.2 48.2 0.0 0.0 7.3 Cinnamomi Ramulus III 5.3 98.0 1.2 23.5 5.7 Polyporus I 0.0 11.5 0.0 5.3 1.4 Polyporus II 0.0 12.7 0.0 0.0 0.9 Cortex Cinnamomi Cortex 2.3 43.7 0.0 0.0 2.9 Total (34) 6.1 40.3 4.7 2.2 6.5

408 Sam Ju Jung et al. 기준초과한약재의탕제전, 후의중금속이행률조사중금속이높게검출된한약재총 23품목 34건에대하여각각탕액을제조하여중금속이행률을알아본결과 (Table 5) 탕액에서의납이행률은 0.0%-43.5% 의범위로나타났다. 납평균이행률은 6.1% 였으며한인진 (43.5%) 을포함한오약 (25.0%), 인진호 (14.2%), 갈근 (16.9%), 아출II(10.3%), 계지I(13.3%) 등이평균값보다높은이행률을보였다. 비소의경우탕제전비소의개별기준을초과한시료는없었으나 탕액에서의이행률이 2.2%- 98% 의범위로나와평균이행률이 40.3% 로상당히높게나타났다. 비소는다른원소들에비해서대부분이행률이높게나타났는데한인진, 인진호, 오약, 아출, 골쇄보, 계지등은 70% 이상의높은이행률을보였다. 카드뮴의경우탕액에서의이행률은 0.0%-14.63% 의범위를보였으며, 평균이행률은 4.7% 로나타났다. 탕제전에카드뮴개별기준을초과했던대부분의시료들이탕제후농도가허용치보다낮은값을보였으며, 납과마찬가지로이행률이현저히저하하는경향을보였다. 수은의경우이행률이 0%-23.53% 의범위로나타났으며, 평균값은 2.2% 로나타났다. 전체평균이행률은 0.21%-17.6% 범위로나타났고평균 6.5% 의이행률을보였다. 시료중애엽, 인진호, 한인진, 오약, 갈근, 계지, 황련, 골쇄보는이행률이 10% 이상으로나와평균보다높은이행률을보였다. 임등 9) 의연구와비교해보면납, 카드뮴, 수은의평균이행률은 10% 이내로서거의비슷한결과를보였으나비소의평균이행률이 26.1% 인결과와는다소차이를보였다. 그러나다른원소에비해비소의평균이행률이높게나온것과거의모든원소에서오약, 황련등이평균값보다높은이행률을보인것은비슷한양상을나타내었다. 이와같은결과로서비소와수은의경우는전체적으로허용한계치를초과하는경우가적어비교적안전한것으로보이며납, 카드뮴의경우탕제후에는중금속함량이현저히떨어져어느정도안전성이확보되어지는것으로나타났다. 그러나비소의이행률이다른원소에비해대부분높게나타나는것에대해서는지속적인모니터링의실시와체계적인관리가필요하겠으며, 향후한약재재배과정중농약의사용으로인해비소의함량에영향을미치는지에대한연구도함께수행되면좋을것으로보인다. 한약은천연물을기원으로하기때문에토양, 수질등주변의환경에의하여영향을많이받으므로약재의산지와기후, 품종, 토양과분석방법간의차이, 생약의약용부위에따라서도다소함량의차이가있어다른문헌과의일률적인비교는어렵다 4). 그리고대부분이한약재를전탕하여복용하고있으며, 전탕하는과정에서약재성분인불용성및난용성의무기염, 탄닌등이금속과반응하게되므로최종적으로사람이복용하는형태인탕제의금속함량은달라질수있다 18). 따라서보다안전하고구체적인품질관리를위해서는한약의조제방식에따른금속농도의변화를고 려할필요가있으며, 이를위한연구가보강, 수행되어야할것으로사료된다. 요약 본연구에서는국내에서유통되는한약재 132품목 1047건을대상으로하여납, 비소, 카드뮴, 수은의함량을측정하고오염정도를약용부위별로비교분석하였다. 시료는 microwave 법을이용하여분해하였으며납, 카드뮴, 비소는유도결합플라즈마질량분석기 (ICP/MS) 를이용하여분석하였고수은은수은분석기를이용하여측정하였다. 전체시료의중금속평균함량은납 0.870 (ND-69.200) mg/kg, 비소 0.148 (ND-2.965) mg/kg, 카드뮴 0.092 (ND-2.010) mg/kg, 수은 0.007 (ND-0.137) mg/kg으로나타났다. 또한납, 비소, 카드뮴, 수은을합한전체중금속함량을기준으로한약용부위별중금속합계평균함량은줄기류 2.046 (0.065-4.474), 잎류 1.886 (0.048-10.404), 화류1.874 (0.052-5.393), 표피류 1.377 (0.011-4.837), 뿌리류 1.165 (0.012-70.111), 뿌리줄기류 1.116 (0.016-5.490, 열매류 0.838 (0.017-4.527), 버섯류 0.729 (0.013-4.953), 종자류 0.646 (0.006-4.416) 의순으로나타났다. 중금속평균함량은뿌리류를제외한다른부위에서모두국내산한약재보다수입산한약재에서다소높게나타났다. 기준을초과한이들시료를탕액으로만들어탕제전후의중금속함량을측정하고이행률을산정한결과이행률평균값은납 6.1%, 비소 40.3%, 카드뮴 4.7%, 수은 2.2% 로나타나탕제후에중금속함량이현저히떨어지는결과를보였다. 본연구결과는시중유통중인한약재에대한보다세부적인중금속기준설정과구체적인품질관리를위한참고자료로활용될수있을것으로기대된다. 감사의글 본연구는서울시보건환경연구원강북농수산물검사소의지원으로이루어졌으며, 김동규, 김욱희, 신영, 김화순, 이성득선생님께감사드립니다. 참고문헌 1. Kim, M.K., Hur, M.H., Lee, C.H., Jin, J.S., Jin, S.K., Lee, Y.J.: Monitoring of residual sulfur dioxide in herbal medicines. Kor. J. Pharmacogn., 35, 276-282 (2004). 2. Sohn, E.S., Kim, S.W., Kang, J.S., Lee, S.P.: Domestic R&D trend analysis of functional food using medical plants. Applied Chem., 8, 470-473 (2004). 3. Chun, O.K.: A study on the contents of inorganic metals and the safety in botanical pills. J. Food Hyg. Safety., 16, 300-307 (2001). 4. Go, B.S.: Study on security of quality control and safety in

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